Positive photosensitive composition

ABSTRACT

A positive photosensitive composition comprising (A) an acid generator that generates an acid upon irradiation of an actinic ray or radiation, (B) a resin that has a monocyclic or polycyclic alicyclic hydrocarbon structure and is decomposed by the action of an acid to increase solubility in an alkali developing solution, and (C) a specific basic compound.

FIELD OF THE INVENTION

The present invention relates to a positive photosensitive compositionused in the production process of semiconductor devices, for example,IC, in the production of circuit substrates for liquid crystals orthermal heads, and in other photofabrication processes. Morespecifically, the present invention pertains to a positivephotosensitive composition suitable for use a far ultraviolet ray of notmore than 250 nm as a light source for exposure.

BACKGROUND OF THE INVENTION

A chemically amplified positive resist composition is a patternformation material in which an acid is generated in the exposed areaupon irradiation of radiation, for example, a far ultraviolet ray, andsolubility in a developer between the exposed area and unexposed area isdifferentiated by a reaction using the acid as a catalyst, whereby apattern is formed on a substrate.

Since the composition is mainly composed of a resin having as a basicskeleton, polythydroxystyrene) that has a small absorption in a regionof 248 nm, a good pattern with high sensitivity and high resolution isformed, when a KrF excimer laser is used as a light source for exposure.Thus, the composition is superior to a conventional resist compositionusing a naphthoquinonediazide/novolac resin.

When a light source having a shorter wavelength, e.g., an ArF excimerlaser (193 nm) is used for exposure, on the other hand, since anaromatic group-containing compound essentially has a large absorption ina region of 193 nm, the above-described chemically amplified compositionis still insufficient.

The use of poly(meth)acrylate as a polymer having a small absorption ina wavelength range of 193 nm is described in J. Vac. Sci. Technol., B9,3357(1991). The polymer has, however, a problem in that resistance todry etching ordinarily performed in a semiconductor production processis low in comparison with conventional phenolic resins having anaromatic group.

Also, a triarylsulfonium salt acid generator and a phenacylsulfoniumsalt acid generator are known as acid generators for chemicallyamplified positive resist composition. However, these acid generatorsare low in sensitivity, since the . triarylsulfonium salt acid generatorhas a large absorption at a wavelength of 193 nm and thephenacylsulfonium salt acid generator is inferior in the acid-generatingproperty. According to the request on the miniaturization ofsemiconductor chips in recent years, patterns of semiconductor reach toa fine range of from 0.13 to 0.35 μm. However, conventional resistcompositions have a problem in that the resolution of pattern is poorowing to factors, for example, edge roughness of line pattern. The term“line edge roughness” used herein means unevenness of edge which resultsfrom irregular fluctuation of an edge of top portion and an edge ofbottom portion in the direction vertical to the line due to thecharacteristics of resist, when the pattern is observed from just above.

Further, other characteristics, for example, halftone exposure aptitudeare not satisfied according to conventional techniques. The term“halftone exposure aptitude” used herein means that when the exposure isperformed using a halftone phase sift mask, sidelobe, which is aphenomenon wherein a hole is apt to be made due to weakening of surfacein the unexposed area, does not occur or hardly occur. The halftoneexposure aptitude is also referred to as sidelobe resistance. Moreover,it is also desired to restrain development defect in conventional resistcomposition. For instance, resist compositions containing anacid-decomposable resin having an alicyclic hydrocarbon structure and asingle basic compound are described, for example, in JP-A-10-111569 andJP-A-11-305444 (the term “JP-A” as used herein means an “unexaminedpublished Japanese patent application”). However, there is room forimprovement, for example, in the edge roughness of pattern anddevelopment defect.

SUMMARY OF THE INVENTION

Therefore, an object of the present invention is to provide a positivephotosensitive composition in which edge roughness of pattern isimproved and development defect is restrained.

Another object of the present invention is to provide a positivephotosensitive composition that is excellent in halftone exposureaptitude (or sidelobe resistance).

Other objects of the present invention will become apparent from thefollowing description.

The above-described objects of, the present invention are accomplishedby the positive photosensitive compositions described below.

1. A positive photosensitive composition comprising (A) an acidgenerator that generates an acid upon irradiation of an actinic ray orradiation, (B) a resin that has a monocyclic or polycyclic alicyclichydrocarbon structure and is decomposed by the action of an acid toincrease solubility in an alkali developing solution, and (C) a basiccompound, wherein the basic compound is (C-1) a Amixture of at least twobasic compounds having different structures, (C-2) a basic compoundcontaining a substituted or unsubstituted aliphatic hydrocarbon grouphaving not less than 8 carbon atoms, or (C-3) a basic compound selectedfrom an oxygen-containing primary aliphatic amine, an oxygen-containingsecondary aliphatic amine and an oxygen-containing tertiary aliphaticamine.

2. A positive photosensitive composition comprising (A) an acidgenerator that generates an acid upon irradiation of an actinic ray orradiation, (B) a resin that has a monocyclic or polycyclice alicyclichydrocarbon structure and is decomposed by the action of an acid toincrease solubility in an alkali developing solution, and (C-1) amixture of at least two basic compounds having different structures.

3. A positive photosensitive composition comprising (A) an acidgenerator that generates an acid upon irradiation of an actinic ray orradiation, (B) a resin that has a monocyclic or polycyclic alicyclichydrocarbon structure and is decomposed by the action of an acid toincrease solubility in an alkali developing solution, and (C-2) a basiccompound containing a substituted or unsubstituted aliphatic hydrocarbongroup having not less than 8 carbon atoms.

4. A positive photosensitive composition comprising (A) an acidgenerator that generates an acid upon irradiation of an actinic ray orradiation, (B) a resin that has a monocyclic or polycyclic alicyclichydrocarbon structure and is decomposed by the action of an acid toincrease solubility in an alkali developing solution, and (C-3) a basiccompound selected from an oxygen-containing primary aliphatic amine, anoxygen-containing secondary aliphatic amine and an oxygen-containingtertiary aliphatic amine.

5. The positive photosensitive composition as described in item (4)above, wherein the positive photosensitive composition .furthercomprises (C′) a basic compound that does not contain an oxygen atom.

6. The positive photosensitive composition as described in item (1)above, wherein the positive photosensitive composition further comprises(D) a fluorine and/or silicon surface active agent.

7. The positive photosensitive composition as described in item (1)above, wherein the positive photosensitive composition further comprises(F) a dissolution inhibiting low molecular weight compound having agroup capable of being decomposed by the action of an acid to increasesolubility in an alkali developing solution and having a molecularweight of not more than 3,000.

8. The positive photosensitive composition as described in item (1)above, wherein the positive photosensitive composition further comprises(E) a mixed solvent composed of a solvent containing a hydroxy group anda solvent containing no hydroxy group.

DETAILED DESCRIPTION OF THE INVENTION

The positive photosensitive composition according to the presentinvention will be described in more detail below.

<<(A) Acid generator>>

The photosensitive composition of the present invention includes an acidgenerator (or a photo-acid generator) that generates an acid uponirradiation of an actinic ray or radiation of component (A).

Such a photo-acid generator can be appropriately selected fromphotoinitiators for photo-catiqnic polymerization, photoinitiators forphoto-radical polymerization, photo-achromatic agents for dyes,photo-discoloring agents, known compounds generating an acid uponirradiation of an actinic ray or radiation used for a microresist, andmixtures thereof

Examples of such photo-acid generators include an onium salt, forexample, a diazonium salt, an ammonium salt, a phospbonium salt, aniodonium salt, a sulfonium salt, a selenonium salt or an arsonium salt,an organic halogeno compound, an organo-metal/organic halide, aphoto-acid generator having an Q-nitrobenzyl type protective group, acompound generating a sulfonic acid upon photolysis, which isrepresented by an iminosulfonate, and a disulfone compound.

Also, polymer compounds in which a group or compound generating an acidupon irradiation of an actinic ray or radiation is introduced into themain chain or aide chain thereof, for example, compounds as described,for example, in U.S. Pat. No. 3,849,137, West German Patent 3,914,407,JP-A-63-26653, JP-A-55-164824, JP-A-62-69263, JP-A-63-146038,JP-A-63-163452, JP-A-62-153853 and JP-A-63-146029 may be used.

Further, compounds generating an acid with light as described, forexample, in U.S. Pat. No. 3,779,778 and European Patent 126,712 may beused.

Of the compounds decomposing upon irradiation of an actinic ray orradiation to generate an acid, those, which can be particularlyeffectively used, are described below.

-   (1) Iodonium salt represented by formula (PAG1) shown below or    sulfonium salt represented by formula (PAG2) shown below:

In formulae (PAG1) and (PAG2), Ar¹ and Ar², which may be the same ordifferent, each independently represent a substituted or unsubstitutedaryl group. Preferred examples of the substituent include an alkylgroup, a haloalkyl group, a cycloalkyl group, an aryl group, an alkoxygroup, a.nitro group, a carboxy group, an alkoxycarbonyl group, ahydroxy group, a mercapto group and a halogen atom.

R²⁰³, R²⁰⁴ and R²⁰⁵, which may be the same or different, eachindependently represents a substituted or unsubstituted alkyl group or asubstituted or unsubstituted aryl group, preferably an aryl group havingfrom 6 to 14 carbon atoms, an alkyl group having from 1 to 8 carbonatoms, or a substituted derivative thereof. Preferred examples of thesubstituent include, for the aryl group, an alkoxy group having from 1to 8 carbon atoms, an alkyl group having from 1 to 8 carbon atoms, anitro group, a carboxy group, a hydroxy group and a halogen atom, andfor the alkyl group, an alkoxy group having from 1 to 8 carbon atoms, acarboxy group and an alkoxycarbonyl group.

Z⁻represents a counter anion. Examples of the counter anion include BF₄⁻, AsF₆ ⁻, PF₆ ⁻, SbF₆ ⁻, SiF₆ ²⁻, ClO₄ ⁻, a perfluoroalkane sulfonicacid anion, e.g., CF₃SO₃ ⁻, pentafluorobenzene sulfonic acid anion, acondensed polynucleic aromatic sulfonic anion, e.g.,naphthalene-1-sulfonic acid anion, an anthraquinone sulfonic acid anionand a dye containing a sulfonic group, however, the present inventionshould not be construed as being limited thereto.

Two of R²⁰³, R²⁰⁴ and R²⁰⁵ or Ar¹ and Ar² may be combined with eachother through a single bond or a substituent.

Specific examples of such compounds are set forth below, but the presentinvention should not be construed as being linited thereto.

The onium salts represented by formulae (PAG1) and (PAG2) are known andcan be synthesized by methods described, for example, in U.S. Pat. Nos.2,807,648 and 4,247,473 and JP-A-53-101331.(2) Disulfone derivative represented by formula (PAG3) shown below oriminosulfonate derivative represented by formula (PAG4) shown below;

In formulae (PAG3) and (PAG4), Ar³ and Ar⁴, which may be the same ordifferent, each independently represent a substituted or unsubstitutedaryl group; R²⁰⁶ represents a substituted or unsubstituted alkyl groupor a substituted or unsubstituted aryl group; and A represents asubstituted or unsubstituted alkylene group, a substituted orunsubgtituted alkenylene group or a substituted or unsubstituted arylenegroup.

Specific examples of such compounds are set forth below, but the presentinvention should not be construed as being limited thereto.

(3) Diazodisulfone derivative represented by formula (PAG5) shown below:

In formula (PAC5), R represents a straight chain, branched or cyclicalkyl group or a substituted or unsubstituted aryl group.

Specific examples of such compounds are set forth below, but the presentinvention should not be construed as being limited thereto.

In addition to the compounds described above, a phenacylsulfoniumderivative represented by formula (I) shown below is also effectivelyused as the acid generator of component (A) according to the presentinvention.

In formula (I), R₁ to R₅, which may be the same or different, eachrepresent a hydrogen atom, an alkyl group, an alkoxy group, a nitrogroup, a halogen atom, an alkoxycarbonyl group or an aryl group, or atleast two of R₁ to R3 may be combined with each other to form a ringstructure,

R₆ and R₇, which may be the same or different, each represent a hydrogenatom, an alkyl group, a cyano group or an aryl group,

Y₁ and Y₂, which may be the same or different, each represent an alkylgroup, an aryl group, an aralkyl group or an aromatic group containing ahetero atom, or Y₁ and Y₂ may be combined with each other to form aring,

Y₃ represents a single bond or a divalent connecting group,

X⁻represents a non-nucleophilic anion, provided that at least one of R₁to R₅ and at least one of Y₁ and Y₂ are combined with each other to forma ring or at least one of R₁ to R₅ and at least one of R₆ and R₇ arecombined with each other to form a ring.

Any of R₁ to R₇ and Y₁ to Y₂ is bonded through a connecting group toform a compound having two or more structures represented by formula(I).

The alkyl group represented by any one of R₁ to R₇ is a substituted orunsubstituted alkyl group, and preferably an alkyl group having from 1to 5 carbon atoms. examples of the unsubstituted alkyl group includenethyl, ethyl, propyl, n-butyl, sec-butyl and tert-butyl groups.

The alkoxy group represented by any one of R₁ to R₅ or the alkoxy groupin the alkoxycarbonyl group represented by any one of R₁ to R₅ is asubstituted or unsubstituted alkoxy group, and preferably an alkoxygroup having from 1 to 5 carbon atoms. Examples of the unsubstitutedalkoxy group include methoxy, ethoxy, propoxy and butoxy groups.

The aryl group represented by any one of R₁ to R₇, Y₁ and Y₂ is asubstituted or unsubstituted aryl group, and preferably an aryl grouphaving from 6 to 14 carbon atoms. Examples of the unsubstituted arylgroup include phenyl, tolyl and naphthyl groups.

The halogen atom represented by any one of R₁ to R₅ includes, forexample, fluorine, chlorine, bromine and iodine atoms.

The alkyl group represented by Y₁ or Y₂ is a substituted orunsubstituted alkyl group, and preferably an alkyl group having from 1to 30 carbon atoms. Examples of the unsubstituted alkyl group include astraight chain or branched alkyl group, e.g., methyl, ethyl, propyl,n-butyl, sec-butyl or tert-butyl group and a cyclic alkyl group, e.g.,cyclopropyl, cyclopentyl, cyclohexyl, adamantly, norbornyl or bornylgroup,

The aralkyl group represented by Y₁ or Y₂ is a substituted orunsubstituted aralkyl group, and preferably an aralkyl group having from7 to 12 carbon atoms. Examples of the unsubstituted aralkyl groupinclude benzyl, phenethyl and cumyl groups.

The aromatic group containing a hetero atom represented by Y₁ or Y₂ isan aromatic group, for example, an aryl group having from 6 to 14 carbonatoms, containing a hetero atom, for example, a nitrogen atom, an oxygenatom or a sulfur atom, and includes a substituted or unsubstitutedaromatic group containing a hetero atom. Examples of the unsubstitutedaromatic group containing a hetero atom include a heterocyclic aromatichydrocarbon group, e.g., furyl, thienyl, pyrrolyl, pyridyl or indolylgroup.

Y₁ and Y₂ may be combined with each to form a ring other together withS⁺ in formula (I).

In such a case, the group formed by connecting Y₁ and Y₂ is an alkylenegroup having from 4 to 10 carbon atoms, preferably butylene, pentyleneor hexylene group, and particularly preferably butylene or pentylenegroup.

The ring formed by connecting Y₁ and Y₂ together with S⁺ in formula (I)may contain a hetero atom.

The alkyl group, alkoxy group, alkoxycarbonyl group, aryl group andaralkyl group may be substituted, for example, with a nitro group, ahalogen atom, a carboxy group, a hydroxy group, an amino group, a cyanogroup or an alkoxy group (preferably an alkoxy group having from 1 to 5carbon atoms), respectively. The aryl group and aralkyl group mayfurther be substituted with an alkyl group (preferably an alkyl grouphaving from 1 to 5 carbon atoms).

The substituent for the alkyl group is preferably a halogen atom.

Y₃ represents a single bond or a divalent connecting group. The divalentconnecting group is preferably an alkylene group which may besubstituted, an alkenylene group which may be substituted, —O—, —S—,—CO—, —CONR— (wherein R represents a hydrogen atom, an alkyl group or anacyl group) or a connecting group formed by combination of two or moreof these groups.

The non-nucleophilic anion represented by X⁻ includes, for example, asulfonic acid anion and a carboxylic acid anion.

The non-nucleophilic anion means an anion having an extremely low.ability for causing a nucleophilic reaction and an anion capable ofcontrolling decomposition with the lapse of time by an intramolecularnucleophilic reaction. By means of the non-nucleophilic anion,preservation stability of the photosensitive composition is improved.

Examples of the sulfonic acid anion include an alkylsulfonic acid anion,an arylsulfonic acid anion and camphorsulfonic acid anion.

Examples of the carboxylic acid anion include an alkylcarboxylic acidanion, an arylcarboxylic acid anion and an aralkylcarboxylic acid anion.

The alkyl group in the alkylsulfonic acid anion is preferably an alkylgroup having from 1 to 30 carbon atoms, for example, methyl, ethyl,propyl, isopropyl, n-butyl, isobutyl, sec-butyl, pentyl, neopentyl,hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl,tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl,eicosyl, cyclopropyl, cyclopentyl, cyclohexyl, adamantly, norbornyl orbornyl group.

The aryl group in the arylsulfonic acid anion is preferably an arylgroup having from 6 to 14 carbon atoms, for example, phenyl, tolyl ornaphthyl group.

The alkyl group and aryl group in the alkylsulfonic acid anion andarylsulfonic acid anion may have a substituent.

Examples of the substituent include a halogen atom, an alkyl group, analkoxy group and an alkylthio group.

The halogen atom includes, for example, chlorine, bromine, fluorine oriodine atoms.

The alkyl group (preferably an alkyl group having from 1 to 15 carbonatoms) includes, for example, methyl, ethyl, propyl, isopropyl, n-butyl,isobutyl, sec-butyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl,decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl,heptadecyl, octadecyl, nonadecyl and eicosyl groups.

The alkoxy group (preferably an alkoxy group having trom 1 to 5 carbonatoms) includes, for example, methoxy, ethoxy, propoxy and butoxygroups.

The alkylthio group (preferably an alkylthio group having from 1 to 15carbon atoms) includes, for example, methylthio, ethylthio, propylthio,isopropylthio, n-butylthio, isobutylthio, sec-butylthio, pentylthio,neopentylthio, hexylthio, heptylthio, octylthio, nonylthio, decylthio,undecylthio, dodecylthio, tridecylthio, tetradecylthio, pentadecylthio,hexadecylthio, heptadecylthio, octadecylthio, nonadecylthio andeicosylthio groups.

The alkyl group, alkoxy group and alkylthio group may further besubstituted with a halogen atom (preferably a fluorine atom).

The alkyl group in the alkylcarboxylic acid anion is same as that in thealkylsulfonic acid anion.

The aryl group in the arylcarboxylic acid anion is same as that in thearylsulfonic acid anion.

The aralkyl group in the aralkylcarboxylic acid anion is preferably anaralkyl group having from 7 to 12 carbon atoms, for example, benzyl,phenetyl, naphthylmethyl or naththylethyl group.

The alkyl group, aryl group and aralkyl group in the alkylcarboxylicacid anion, arylcarboxylic acid anion and aralkylcarboxylic anion mayhave a substituent. Examples of the substituent include those describedfor the arylsulfonic acid anion, for example, a halogen atom, an alkylgroup, an alkoxy group or an alkylthio group.

Other examples of the non-nucleophilic anion include phosphorusfluoride, boron fluoride and antimony fluoride.

In the compound represented by formula (I), at least one of R₁ to R₅ andat least one of Y₁ and Y₂ are combined with each other to form a ring orat least one of R₁ to R₅ and at least one of R₆ and R₇ are combined witheach other to form a ring.

By the formation of ring in the compound represented by formula (I), thesteric configuration of compound is fixed and the photolysis efficiencyof the compound increases.

Further, any of R₁ to R₇ and Y₁ to Y₂ is bonded through a connectinggroup to form a compound having two or more structures represented byformula (I).

Of the compounds represented by formula (I), those represented byformulae (IA) and (IB) described above are preferred.

In formula (IA), R₁ to R₄, R₇, Y₁, Y₂ and X⁻ have the same meanings asdefined in formula (I) respectively, and Y represents a single bond or adivalent connecting group.

In formula (IB), R₁ to R_(4,) R₆, R₇, Y₁ and X⁻ have the same meaningsas defined in formula (I) respectively, and Y represents a single bondor a divelent connecting group.

Y represents a single bond or a divalent connecting group. The divalentconnecting group is preferably an alkylene group which may besubstituted, an alkenylene group which may be substituted, —O—, —S—,—CO—, —CONR— (wherein R represents a hydrogen atom, an alkyl group or anacyl group) or a connecting group formed by combination of two or moreof these groups.

In formula (IA), Y preferably represents an alkylene group, an alkylenegroup containing an oxygen atom or an alkylene group containing a sulfuratom, for example, an ethylene group, a propylene group, —CH₂—O— or—CH₂—S—, and most preferably represents a connecting group for forming a6-membered ring, for example, an ethylene group, —CH₂—O— or —CH₂—S—. Bythe formation of 6-membered ring in the compound, an angle between thecarbonyl plane and the C-S⁺ sigma bond comes up to perpendicularity, anddue to the orbital interaction the photolysis efficiency of the compoundincreases.

The compound represented by formula (IA) can be obtained by a method ofreacting a corresponding α-halo cyclic ketone with a sulfide compound ora method of converting a corresponding cyclic ketone to a silyl enolether and reacting the latter with sulfoxide. The compound representedby formula (IB) can be obtained by a method of reacting an aryl alkylsulfide with an α- or β-halogenated halide.

Specific examples of the compound represented by formula (I) are setforth below, but the present invention should not be construed as beinglimited thereto.

Of specific examples of the acid photo-generator represented by formula(I) described above, Compounds (IA-1) to (IA-30) and (IB-1) to (IB-12)are more preferred.

The compounds represented by formula (I) may be used individually or incombination of two or more thereof.

The content of the compound of component (A) is preferably from 0.1 to20% by weight, more preferably from 0.5 to 10% by weight, and still morepreferably from 1 to 74 by weight, based on the solid content of thepositive photosensitive composition of the present invention.

Of the compounds decomposing upon irradiation of an actinic ray orradiation to generate an acid of component (A) for use in the presentinvention, those particularly preferred are set forth below.

<<(B) Resin Increasing Solubility in an Alkali Developing Solution bythe Action of an Acid (hereinafter, also Referred to as an“Acid-Decomposable Resin”)>>

Any resin that has a monocyclic or polycyclic alicyclic hydrocarbonstructure and is decomposed by the action of an acid to increasesolubility in an alkali developing solution can be used as theacid-decomposable resin of component (B) Preferred examples of the resinof component (B) include resins containing at least one repeating unitselected from a repeating unit having a partial structure including analicyclic hydrocarbon represented by formula (pI), (pII), (pIII), (pIV),(pV) or (pVI) described below and a repeating unit represented byformula (II-AB) described below.

In the above formulae, R₁₁ represents a methyl group, an ethyl group, ann-propyl group, an isopropyl group, an n-butyl group, an isobutyl groupor a sec-butyl group, and Z represents an atomic group necessary forforming an alicyclic hydrocarbon group together with the carbon atom.

R₁₂ to R₁₆ each independently represent a straight chain or branchedalkyl group having from 1 to 4 carbon atoms or an alicyclic hydrocarbongroup, provided that at least one of R₁₂ to R₁₄, and either R₁₅ or R₁₆represents an alicyclic hydrocarbon group.

R₁₇ to R₂₁ each independently represent a hydrogen atom, a straightchain or branched alkyl group having from 1 to 4 carbon atoms or analicyclic hydrocarbon group, provided that at least one of R₁₇ to R₂₁represents an alicyclic hydrocarbon group, and either R₁₉ or R₂₁represents a straight chain or branched alkyl group having from 1 to 4carbon atoms or an alicyclic hydrocarbon group.

R₂₂ to R₂₅ each independently represent a straight chain or branchedalkyl group having from 1 to 4 carbon atoms or an alicyclic hydrocarbongroup, provided that at least one of R₂₂ to R₂₅ represents an alicyclichydrocarbon group, provided that at least one of R₂₂ to R₂₅ representsan alicyclic hydrocarbon group. Alternatively, R₂₃ and R₂₄ may becombined with each other to form a ring.

In formula (II-AB), R₁₁′ and R₁₂′, which may be the same or different,each independently represent a hydrogen atom, a cyano group, a halogenatom or an alkyl group which may have a substituent.

Z′ represents an atomic group necessary for forming an alicyclicstructure, which may be substituted, together with the connected twocarbon atoms (C—C).

Of the repeating units represented by formula (II-AB), those representedby formulae (II-A) and (II-B) shown below are more preferred.

In formulae (II-A) and (II-B), R₁₃′ to R₁₆′, which may be the same ordifferent, each independently represents a hydrogen atom, a halogenatom, a cyano group, —COOH, —COOR₅, a group capable of decomposing bythe action of acid, —C(═O)—X-A′-R₁₇′, an alkyl group which may have asubstituent or a cyclic hydrocarbon group which may have a substituent.

R₅ represents an alkyl group which may have a substituent, a cyclichydrocarbon group which may have a substituent or a group-represented byY.

X represents an oxygen atom, a sulfur atom, —NH—, —NHSO₂— or —NHSO₂NH—.

A′ represents a single bond or a divalent linkage group.

Alternatively, at least two of R₁₃′ to R₁₆′ may be combined with eachother to form a ring. n represents 0 or 1.

R₁₇′ represents —COOH, —COOR₅, —CN, a hydroxy group, an alkoxy groupwhich may have a substituent, —CO—NH—R₆, —CO—NH—SO₂—R₆ or a grouprepresented by Y. R₆ represents an alkyl group which may have asubstituent or a cyclic hydrocarbon group which may have a substituent.

The group represented by Y has the following structure:

wherein R₂₁′ to R₃₀′, which may be the same or different, eachindependently represents a hydrogen atom or an alkyl group which mayhave a substituent, and a and b each represent 1 or 2.

In formulae (pI) to (pVI), the alkyl group for R₁₂ to R₂₅ includes astraight chain or branched alkyl group having from 1 to 4 carbon atoms,which may be substituted. Examples of the alkyl group include methyl,ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butylgroups.

Examples of the substituent for the alkyl group include an alkoxy grouphaving from 1 to 4 carbon atoms, a halogen atom (e.g., fluorine,chlorine, bromine or iodine atom), an acyl group, an acyloxy, group, acyano group, a hydroxy group, a carboxy group, an alkoxycarbonyl groupand a nitro group.

The alicyclic hydrocarbon group in R₁₁ to R₂₅ or the alicyclichydrocarbon group formed by Z and the carbon atoms may be a monocyclicgroup or a polycyclic group, and includes specifically a group havingnot less than 5 carbon atoms and including, for example, a monocyclo,bicyclo, tricyclo or tetracyclo structure. The number of carbon atomsincluded is preferably from 6 to 30, and more preferably from 7 to 25.The alicyclic hydrocarbon group may have a substituent.

Examples of the structure of alicyclic portion in the alicyclichydrocarbon group are set forth below.

Preferred examples of the alicyclic portion for use in the presentinvention include an adamantyl group, a noradamantyl group, a decalinresidue, a tricyclodecanyl group, a tetracyclododecanyl group, anorbornyl group, a cedrol group, a cyclohexyl group, a cycloheptylgroup, a cyclooctyl group, a cyclodecanyl group and a cyclododecanylgroup. Of these groups, an adamantyl group, a decalin residue, anqrbornyl group, a cedrol group, a cyclohexyl group, a cycloheptylgroup, a cyclooctyl group, a cyclodecanyl group and a cyclododecanylgroup are more preferred.

Examples of the substituent for the alicyclic hydrocarbon group includean alkyl group, a substituted alkyl group, a halogen atom, a hydroxygroup, an alkoxy group, a carboxy group and an alkoxycarbonyl group. Thealkyl group is preferably a lower alkyl group, for example, methyl,ethyl, propyl, isopropyl or butyl group, and more preferably methyl,ethyl, propyl or isopropyl group. Examples of the substituent for thesubstituted alkyl group include a hydroxy group, a halogen atom and analkoxy group. The alkoxy group includes an alkoxy group having from 1 to4 carbon atoms, for example, methoxy, ethoxy, propoxy or butoxy group.

The structure represented by any one of formulae (pI) to (pVI) in theresin can be used for protecting an alkali-soluble group. Thealkali-soluble group includes various groups known in the field of art.

Specific examples of the alkali-soluble group include a carboxylic acidgroup, a sulfonic acid group, a phenol group and a thiol group, and acarboxylic acid group and a sulfonic acid group are preferably used.

The alkali-soluble group protected by the structure represented byanyone of formulae (pI) to (pVI) in the resin preferably includes groupsrepresented by the following formulae (pVII) to (pXI):

In the above formulae, R₁₁ to R₂₅ and Z has the same meanings as definedabove, respectively.

A repeating unit having the alkali-soluble group protected by thestructure represented by any one of formulae (pI) to (pVI) in the resinis preferably represented by the following formula (pA):

In the formula, R's, which may be the same or different, each representa hydrogen atom, a halogen atom or a straight chain or branched alkylgroup having from 1 to 4 carbon atoms, which may be substituted,

A represents a single bond, an alkylene group, a substituted alkylenegroup, an ether group, a thioether group, a carbonyl group, an estergroup, an amido group, a sulfonamido group, a urethane group, a ureagroup or a combination of two or more thereof.

R_(a) represents any one of the groups represented by formulae (pI) to(pVI).

Specific examples of the monomer corresponding to the repeating unitrepresented by formula (pA) are set forth below, but the presentinvention should not be construed as being limited thereto.

In formula (II-AB), R₁₁′ and R₁₂′, which may be the same or different,each independently represent a hydrogen atom, a cyano group, a halogenatom or an alkyl group which may have a substituent.

Z′ represents an atomic group necessary for forming an alicyclicstructure, which may be substituted, together with the connected twocarbon atoms (C—C).

The halogen atom for R₁₁′ or R₁₂′ includes, for example, chlorine,bromine, fluorine and iodine atoms.

The alkyl group for each of R₁₁′ and R₁₂′ and R₂₁′ to R₃₀′ includespreferably a straight chain or branched alkyl group having from 1 to 10carbon atoms, more preferably a straight chain or branched alkyl grouphaving from 1 to 6 carbon atoms, and still more preferably methyl,ethyl, propyl, isopropyl, n-butyl, isobutyll sec-butyl and tert-butylgroups.

Examples of the substituent for the alkyl group include a hydroxy group,a halogen atom, a carboxy group, an alkoxy group, an acyl group, a cyanogroup and an acyloxy group. The halogen atom includes chlorine, bromine,fluorine and iodine atoms. The alkoxy group includes an alkoxy grouphaving from 1 to 4 carbon atoms, for example, methoxy, ethoxy, propoxyor butoxy group. The acyl group includes, for example, formyl or acetylgroup, The acyloxy group includes, for example, an acetoxy group.

The atomic group necessary for forming an alicyclic structurerepresented by Z′ is an atomic group necessary for forming a repeatingunit of alicyclic hydrocarbon moiety, which may be substituted. Inparticular, an atomic group necessary for forming a bridged alicyclicstructure, by which a repeating unit of the bridged alicyclichydrocarbon is completed, is preferred.

The skeleton of the bridged alicyclic hydrocarbon formed includes thosedescribed below.

Of the skeletols of the bridged alicyclic hydrocarbon described above,(5), (6), (7), (9), (10), (13), (14), (15), (23), (28), (36), (37), (42)and (47) are preferred.

The skeleton of the alicyclic hydrocarbon may have a substituent.Examples of the substituent include the atoms and groups represented byR₁₃′ to R₁₆′ in formula (II-A) or (II-B).

Of the repeating units containing the bridged alicyclic hydrocarbon,those represented by formulae (II-A) and (II-B) described above are morepreferred.

In formulae (II-A) and (II-B), R₁₃′ to R₁₆′, which may be the same ordifferent, each independently represents a hydrogen atom, a halogenatom, a cyano group, —COOH, —COOR₅, a group capable of decomposing bythe action of acid, —C(═O)—X-A′-R₁₇′, an alkyl group which may have asubstituent or a cyclic hydrocarbon group which may have a substituent.

R₅ represents an alkyl group which may have a substituent, a cyclichydrocarbon group which may have a substituent or a group represented byY.

X represents an oxygen atom, a sulfur atom, —NH—, —NHSO₂— or —NHSO₂NH—.

A′ represents a single bond or a divalent linkage group.

Alternatively, at least two Of R₁₃′ to R₁₆′ may be combined with eachother to form a ring. n represents 0 or 1.

R₁₇′ represents —COOH, —COOR₅, —CN, a hydroxy group, an alkoxy groupwhich may have a substituent, —CO—NN—R₆, —CO—NH—SO₂—R₆ or a grouprepresented by Y. R₆ represents an alkyl group which may have asubstituent or a cyclic hydrocarbon group which may have a substituent.

In the group represented by Y, R₂₁′ to R₃₀′, which may be the same ordifferent, each independently represents a hydrogen atom or an alkylgroup which may have a substituent, and a and b each represent 1 or 2.

In the resin according to the present invention, an acid-decomposablegroup may be incorporated into the above described —C(═O)—X-A′-R₁₇′ oras a substituent for Z′ in formula (II-AB).

The acid-decomposable group includes a group represented by thefollowing formula:—C(═O)—X₁—R₀

In the formula, R₀ represents a tertiary alkyl group, for example,tert-butyl or tert-amyl group, an isobornyl group, an 1-alkoxyethylgroup, for example, 1-ethoxyethyl, 1-butoxyethyl, 1-isobutoxyethyl or1-cyclohexyloxyethyl group, an alkoxymethyl group, for example,1-metoxymethyl or 1-ethoxymethyl group, a 3-oxoalkyl group, atetrahydropyranyl group, a tetrahydrofuryl group, a trialkylsilyl estergroup, a 3-oxocyclohexyl ester group, a 2-methyl-2-adamantyl group or amevalonic lactone residue, and X₁ has the same meaning as X definedabove.

The halogen atom for each of R₁₃′ or R₁₆′ includes, for example,chlorine, bromine, fluorine and iodine atoms.

The alkyl group for each of R₅, R₆ and R₁₃′ to R₁₆′ includes preferablya straight chain or branched alkyl group having from 1 to 10 carbonatoms, more preferably a straight chain or branched alkyl group havingfrom 1 to 6 carbon atoms, and still more preferably methyl, ethyl,propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl groups.

The cyclic hydrocarbon group for each of R₅, R₆ and R₁₃′ to R₁₆′includes a cyclic alkyl group and ai bridged hydrocarbon moiety, forexample, cyclopropyl, cyclopentyl, cyclohexyl, adamantyl,2-methyl-2-adamantyl, norbornyl, bornyl, isobornyl, tricyclodecanyl,dicyclopentenyl, norbornaneepoxy, menthyl, isomenthyl, neomenthyl ortetracyclododecanyl group.

The ring formed by combining at least two of R₁₃′ to R₁₆′ includes aring having from 5 to 12 carbon atoms, for example, cyclopentene,cyclohexene, cycloheptane or cyclooctane ring.

The alkoxy group for R₁₇′ includes an alkoxy group having from 1 to 4carbon atoms, for example, methoxy, ethoxy, propoxy or butoxy group.

Examples of the substituent for the alkyl group, cyclic hydrocarbongroup or alkoxy group described above include a hydroxy group, a halogenatom, a carboxy group, an alkoxy group, an acyl group, a cyano group, anacyloxy group, an alkyl group and a cyclic hydrocarbon group. Thehalogen atom includes, for example, chlorine, bromine, fluorine andiodine atoms. The alkoxy group includes an alkoxy group having from 1 to4 carbon atoms, for example, methoxy, ethoxy, propoxy or butqxy group.The acyl group includes, for example, formyl and acetyl groups. Theacyloxy group includes, for example, an acetoxy group.

The alkyl group and cyclic hydrocarbon group include those describedabove.

The divalent linkage group for A′ includes a single bond, an alkylenegroup, a substituted alkylene group, an ether group, a thioether group,a carbonyl group, an ester group, an amido group, a sulfonamido group, aurethane group, a urea group and a combination of two or more thereof.

Examples of the alkylene group or substituted alkylene group for A′include a group represented by the following formula:—{C(R_(a))(R_(b))}_(r)—

In the formula, R_(a) and R_(b), which may be the same or different,each represent a hydrogen atom, an alkyl group, a substituted alkylgroup, a halogen atom, a hydroxy group or an alkoxy group, and rrepresents an integer of from 1 to 10.

The alkyl group includes preferably a lower alkyl group, for example,methyl, ethyl, propyl, isopropyl or butyl group, and more preferablymethyl, ethyl, propyl or isopropyl group. Examples of the substituentfor the substituted alkyl group include a hydroxy group, a halogen atomand an alkoxy group. The alkoxy group includes an alkoxy group havingfrom 1 to 4 carbon atoms, for example, methoxy, ethoxy, propoxy orbutoxy group. The halogen atom includes, for example, chlorine, bromine,fluorine and iodine atoms.

In the resin of component (B) according to the present invention, theacid-decomposable group may be incorporated into at least one repeatingunit selected from of the repeating unit having a partial structureincluding an alicyclic hydrocarbon represented by formula (pI), (pII),(pIII), (pIV), (pV) or (pVI), the repeating unit represented by formula(II-AB), and a repeating unit of a copolymerization component describedhereinafter.

Various atoms and groups represented by R₁₃′ to R₁₆′ in formula (II-A)or (II-B) constitute substituents for the atomic group necessary forforming an alicyclic structure or a bridged alicyclic structurerepresented by Z′ in formula (II-AB),

Specific examples of the repeating unit represented by formula (II-A) or(II-B) are set forth below as [II-1] to [II-175], but the presentinvention should not be construed as being limited thereto.

The acid-decomposable resin of component (B) according to the presentinvention may further contain a repeating unit having a lactonestructure represented by the following formula (IV);

In formula (IV), R_(1a) represents a hydrogen atom or a methyl group.

W₁ represents a single bond, an alkylene group, an ether group, athioether group, a carbonyl group, an ester group or a combination oftwo or more of thereof.

R_(a1), R_(b1), R_(c1), R_(d1) and R_(e1), which may be the same ordifferent, each independently represent a hydrogen atom or an alkylgroup having from 1 to 4 carbon atoms. m and n, which may be the same ordifferent, each independently represent an integer of from 0 to 3,provided that the sum total of m and n is from 2 to 6.

The alkyl group having from 1 to 4 carbon atoms represented by R_(a1),R_(b1), R_(c1), R_(d1) or R_(e1) includes, for example, methyl, ethyl,propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl groups.

The alkylene group represented by W₁ in formula (IV) includes a grouprepresented by the following formula:—{C(Rf)(Rg)}r₁-

In the above formula, Rf and Rg, which may be the same or different,each represent a hydrogen atom, an alkyl group, a substituted alkylgroup, a halogen atom, a hydxoxy group or an alkoxy group, and r₁represents an integer of from 1 to 10.

The alkyl group is preferably a lower alkyl group, for example, methyl,ethyl, propyl, isopropyl or butyl group, more preferably methyl, ethyl,propyl or isopropyl group. A substituent for the substituted alkyl groupincludes, for example, a hydroxy group, a halogen atom and an alkoxygroup. The alkoxy group includes an alkoxy group having from 1 to 4carbon atoms, for example, methoxy, ethqxy, propoxy or butoxy group. Thehalogen atom includes, for example, chlorine, bromine, fluorine andiodine atoms.

Examples of further substituent for the alkyl group include a carboxygroup, an acyloxy group, a cyano group, an alkyl group, a substitutedalkyl group, a halogen atom, a hydroxy group, an alkoxy group, asubstituted alkoxy group, an acetylamido group, an alkoxycarbonyl groupand an acyl group.

The alkyl group includes a lower alkyl group, for example, methyl,ethyl, propyl, isopropyl, butyl, cyclopropyl, cyclobutyl or cyclopentylgroup. A substituent for the substituted alkyl group includes, forexample, a hydroxy group, a halogen atom and an alkoxy group. Asubstituent for the substituted alkoxy group includes, for example, analkoxy group. The alkoxy group includes an alkoxy group having from 1 to4 carbon atoms, for example, methoxy, ethoxy, propoxy or butoxy group.The acyloxy group includes, for example, an acetoxy group. The halogenatom includes, for example, chlorine, bromine, fluorine and iodineatoms.

Specific examples of the repeating unit represented by formula (IV) areset forth below, but the present invention should not be construed asbeing limited thereto.

Of the specific examples of the repeating unit represented by formula(IV), (IV-17) to (IV-36) are preferred in view of more improved exposuremargin.

Further, the repeating units represented by formula (IV) wherein anacrylate structure is included are preferred from a standpoint of goodedge roughness.

The resin of component (B) according to the present invention mayfurther contain a repeating unit having a group represented by any oneof the following formulae (V-1) to (V-4):

In formulae (V-1) to (V-4), R_(1b), R_(2b), R_(3b), R_(4b) and R_(5b),which may be the same or different, each independently represent ahydrogen atom, an alkyl group which may be substituted, a cycloalkylgroup which may be substituted or an alkenyl group which may besubstituted, or two of R_(1b), R_(2b), R_(3b), R_(4b) and R_(5b), may becombined with each other to form a ring.

The alkyl group represented by any one of R_(1b), R_(2b), R_(3b), R_(4b)and R_(5b) in formulae (V-1) to (V-4) includes a straight chain orbranched alkyl group which may be substituted. The straight chain orbranched alkyl group includes preferably a straight chain or branchedalkyl group having from 1 to 12 carbon atoms, more preferably a straightchain or branched alkyl group having from 1 to 10 carbon atoms, andstill more preferably methyl, ethyl, propyl, isopropyl, n-butyl,isqbutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl anddecyl groups.

The cycloalkyl group represented by any one of R_(1b), R_(2b), R_(3b),R_(4b) and R_(5b) in formulae (V-1) to (V-4) includes preferably acycloalkyl group having from 3 to 8 carbon atoms, for example,cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl group.

The alkenyl group represented by any one of R_(1b), R_(2b), R_(3b),R_(4b) and R_(5b) in formulae (V-1) to (V-4) includes preferably analkenyl group having from 2 to 6 carbon atoms, for example, vinyl,propenyl, butenyl or hexenyl group.

The ring formed by combining two of R_(1b), R_(2b), R_(3b), R_(4b) andR_(5b) in any one of formulae (V-1) to (V-4) includes preferably a3-membered to 8-membered ring, for example, cyclopropane, cyclobutane,cyclopentane, cyclohexane or cyclooctane ring.

The group represented by R_(1b), R_(2b), R_(3b), R_(4b) and R_(5b) informulae (V-1) to (V-4) can be bonded to any one of the carbon atomsconstituting the cyclic structure.

Preferred examples of the substituent for the alkyl group, cycloolkylgroup and alkenyl group described above include an alkoxy group havingfrom 1 to 4 carbon atoms, a halogen atom (e.g., fluorine, chlorine,bromine or iodine atom), an acyl group having from 2 to 5 carbon atoms,an acyloxy group having from 2 to 5 carbon atoms, a cyano group, ahydroxy group, a carboxy group, an alkoxycarbonyl group having from 2 to5 carbon atoms and a nitro group.

Examples of repeating unit having the group represented by any one offormulae (V-1) to (V-4) include a repeating unit represented by formula(II-A) or (II-B) described above wherein one of R₁₃′ to R₁₆′ has thegroup represented by any one of formulae (V-1) to (V-4), for example, R₅of —COOR₅ is the group represented by any one of formulae (V-1) to(V-4), and a repeating unit represented by formula (AI) shown below.

In formula (AI), R_(b0) represents a hydrogen atom, a halogen atom, asubstituted or unsubstituted alkyl group having from 1 to 4 carbonatoms. Preferred examples of the substituent for the alkyl grouprepresented by R_(b0) include the preferred examples of substituent forthe alkyl group represented by R_(1b) in any one of formulae (V-1) to(V-4) described above.

The halogen atom represented by R_(b0) includes fluorine, chlorine,bromine and iodine atoms. R_(b0) is preferably a hydrogen atom.

A′ in formula (AI) represents a single bond, an ether group, an estergroup, a carbonyl group, an alkylene group or a divalent group formed bycombining these groups.

B₂ in formula (AI) represents the group represented by any one offormulae. (V-1) to (V-4).

Examples of the divalent group formed by combination of the groupsrepresented by A′ includes groups represented by the following formulae:

In the above-described formulae, R_(ab) and R_(bb), which may be thesame or different, each represent a hydrogen atom, an alkyl group, asubstituted alkyl group, a halogen atom, a hydroxy group or an alkoxygroup.

The alkyl group represented by any one of R_(ab) and R_(bb) ispreferably a lower alkyl group, for example, methyl, ethyl, propyl,isopropyl or butyl group, and more preferably methyl, ethyl, propyl orisoprqpyl group. A substituent for the substituted alkyl group includesa hydroxy group, a halogen atom and an alkoxy group having from 1 to 4carbon atoms.

The alkoxy group includes an alkoxy group having from 1 to 4 carbonatoms, for example, methoxy, ethoxy, propoxy or butoxy group. Thehalogen atom includes, for example, chlorine, bromine, fluorine andiodine atoms. r1 represents an integer of from 1 to 10, and preferablyfrom 1 to 4. m represents an integer of from 1 to 3, and preferably 1 or2.

Specific examples of the repeating unit represented by formula (AI) areset forth below, but the present invention should not be construed asbeing limited thereto.

The acid-decomposable resin of component (B) according to the presentinvention may further contain a repeating unit represented by thefollowing formula (VI):

In formula (VI), A₆ represents a single bond, an alkylene group, acycloalkylene group, an ether group, a thioether group, a carbonylgroup, an ester group or a combination of two or more thereof.

R_(6a) represents a hydrogen atom, an alkyl group having from 1 to 4carbon atoms, a cyano group or a halogen atom.

The alkylene group for A₆ in formula (VI) includes a group representedby the following formula:—{C(Rnf)(Rng)}r-

In the above formula, Rnf and Rng, which may be the same or different,each represent a hydrogen atom, an alkyl group, a substituted alkylgroup, a halogen atom, a hydroxy group or an alkoxy group, and rrepresents an integer of from 1 to 10.

The alkyl group is preferably a lower alkyl group, for example, methyl,ethyl, propyl, isopropyl or butyl group, and more preferably methyl,ethyl, propyl or isopropyl group. A substituent for the substitutedalkyl group includes, for example, a hydroxy group, a halogen atom andan alkoxy group. The alkoxy group includes an alkoxy group having from 1to 4 carbon atoms, for example, methoxy, ethoxy, propoxy or butoxygroup. The halogen atom includes, for example, chlorine, bromine,fluorine and iodine atoms.

The cycloalkylene group represented by A₆ in formula (VI) includes acycloalkylene group having from 3 to 10 carbon atoms, for example,cyclopentylene, cyclohexylens or cyclooctylene group.

In formula (VI), the bridged alicyclic group including Z₆ may have oneor more substituents. Examples of the substituent include a halogenatom, an alkoxy group (preferably an alkoxy group having from 1 to 4carbon atoms), an alkoxycarbonyl group (preferably an alkoxycarbonylgroup having from 1 to 5 carbon atoms), an acyl group (for example,formyl or benzyl group), an acyloxy group (for example,propylcarbonyloxy or benzoyloxy group), an alkyl group (preferably analkyl group having from 1 to 4 carbon atoms), a carboxy group, a hydroxygroup and an alkylsulfonylsulfamoyl group (for example, —CONHSO₂CH₃).The alkyl group as the substituent may further be substituted with ahydroxy group, a halogen atcm or an alkoxy group (preferably an alkoxygroup having from 1 to 4 carbon atoms),

The oxygen atom of the ester group connected to A₆ in formula (VI) canbe bonded to any one of the carbon atoms constituting the bridgedalicyclic structure containing Z₆.

Specific examples of the repeating unit represented by formula (VI) areset forth below, but the present invention should not be construed asbeing limited thereto.

The resin of component (B) according to the present invention mayfurther contain a repeating unit having a group represented by thefollowing formula (VIII):

In formula (VII), R_(2c), R_(3c) and R_(4c), which may be the same ordifferent, each represent a hydrogen atorm or a hydroxy group, providedthat at least one of R_(2c), R_(3c) and R_(4c) represents a hydroxygroup.

The group represented by formula (VII) is preferably a dihydroxy body ora monohydroxy body, and more preferably a dihydroxy body.

Examples of the repeating unit having the group represented by formulae(VII) include a repeating unit represented by formula (II-A) or (II-B)described above wherein one of R₁₃′ to R₁₆′ has the group represented byformula (VII), for example, R₅ of —COOR₅ is the group represented byformula (VII), and a repeating unit represented by formula the followingformula (AII):

In formula (AII), R_(1c) represents a hydrogen atom or a methyl group,and R_(2c), R_(3c) and R_(4c), which may be the same or different, eachindependently represents a hydrogen atom or a hydroxy group, providedthat at least one of R_(2c), R_(3c) and R_(4c) represents a hydroxygroup.

Specific examples of the repeating unit represented by formula (AII) areset forth below, but the present invention should not be construed asbeing limited thereto.

The resin of component (B) according to the present invention mayfurther contain a repeating unit having a group represented by thefollowing formulae (VIII):

In formula (VIII), Z₂ represents —O— or —N(R₄₁)—, R₄₁ represents ahydrogen atom, a bydroxy group, an alkyl group, a haloalkyl group or—O—SO₂—R₄₂, and R₄₂ represents an alkyl group, a haloakyl group, acycloalkyl group or a camphol residue.

Examples of the alkyl group represented by R₄₁ or R₄₂ include preferablya straight chain or branched alkyl group having form 1 to 10 carbonatoms, more preferably a straight chain or branched alkyl group havingform 1 to 6 carbon atoms, and still more preferably methyl, ethyl,propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl groups.

Examples of the haloalkyl group represented by R₄₁ or R₄₂ includetrifluoromethyl, nonafluorobutyl, pentadecafluorooctyl andtrichloromethyl groups.

Examples of the cycloalkyl group represented by R₄₂ include cyclopentyl,cyclohexyl and cyclooctyl groups.

The alkyl group and haloalkyl group represented by R₄₁ or R₄₂ and thecycloalkyl group and camphol residue represented by R₄₂ may have one ormore substituents.

Examples of the substituent for the alkyl group, haloalkyl group,cycloalkyl group and camphor residue include a hydroxy group, a carboxygroup, a cyano group, a halogen atom (e.g., chlorine, bromine, fluorineor iodine atom), an alkoxy group (preferably an alkoxy group having from1 to 4 carbon atoms, e.g., methoxy, ethoxy, propoxy or butoxy group), anacyl group (preferably an acyl group having from 2 to 5 carbon atoms,e.g., formyl or acetyl group), an acylogy group (preferably an acyloxygroup having from 2 to 5 carbon atoms, e.g., acetoxy group) and an arylgroup (preferably an aryl group having from 6 to 14 carbon atoms, e.g.,phenyl group).

Specific examples of the repeating unit represented by formula (VIII)are set forth below as formulae [I′-1] to [I′-7], but the presentinvention should not be construed as being limited thereto.

The acid-decomposable resin of component (B) according to the presentinvention may contain various repeating units in addition to therepeating units described above for the purposes of adjusting dryetching resistance, standard developing solution aptitude, adhesion tosubstrate, resist profile, and other characteristics ordinarily requiredfor resist, for example, resolution, heat resistance and sensitivity.

Examples of such repeating units include repeating units correspondingto monomers described below, but the present invention should not beconstrued as being limited thereto.

The introduction of additional repeating unit makes possible the minutecontrol of characteristics required for the acid-decomposable resin,particularly (1) solubility in a coating solvent, (2) film formingproperty (glass transition temperature), (3) developing property withalkali, (4) reduction in a film thickness (hydrophobicity, selection ofalkali-soluble group), (5) adhesion of the unexposed area to asubstrate, and (6) dry etching resistance.

Examples of such monomers include compounds having oneaddition-polymerizable unsaturated bond, for example, acrylates,methacrylate, acrylamides, methacrylamides, allyl compound, vinyl ethersand vinyl esters.

Specific examples of the monomer include an acrylate, for example, analkyl acrylate (preferably an alkyl acrylate containing an alkyl grouphaving from 1 to 10 carbon atoms), e.g., methyl acrylate, ethylacrylate, propyl acrylate, amyl acrylate, cyclohexyl acrylate,ethylhexyl acrylate, octyl acrylate, tert-octyl acrylate, chloroethylacrylate, 2-hydroxyethyl acrylate, 2,2-dimethylhydroxypropyl acrylate,5-hydroxypentyl acrylate, trimethylolpropane monoacrylate,pentaerythritol monoacrylate, benzyl acrylate, methoxy-benzyl acrylate,furfuryl acrylate or tetrahydrofurfuryl acrylate; a methacrylate, forexample, an alkyl methacrylate (preferably an alkyl methacrylatecontaining an alkyl group having form 1 to 10 carbon atoms), e.g.,methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropylmethacrylate, amyl methacrylate, hexyl methacrylate, cyclohexylmethacrylate, benzyl methacrylate, chlorobenzyl methacrylate, octylmethacrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate,5-hydroxypentyl methacrylate, 2,2-dimethyl-3-hydroxypropyl methacrylate,trimethylolpropane monomethacrylate, pentaerythritol monomethacrylate,furfuryl methacrylate or tetrahydrofurfuryl methacrylate; an acrylamide,for example, acrylamide, an N-alkylacrylamide (the alkyl group of whichis an alkyl group having from 1 to 10 carbon atoms, e.g., methyl, ethyl,propyl, butyl, tert-butyl, heptyl, octyl, cyclohexyl or hydroxyethylgroup), an N,N-dialkylacrylamide (the alkyl group of which is an alkylgroup having form 1 to 10 carbon atoms, e.g., methyl, ethyl, butyl,isobutyl, ethylhexyl or cyclohexyl group),N-hydroxyethyl-N-methylacrylamide andN-2-acetamidoethyl-N-acetylacrylamide; a methacrylamide, for example,methacrylamide, an N-alkylmethacrylamide (the alkyl group of which is analkyl group having from 1 to 10 carbon atoms, e.g., methyl, ethyl,tert-butyl, ethylhexyl, hydroxyethyl or cyclohexyl group), anN,N-dialkylmethacrylamide (the alkyl group of which includes, e.g.,ethyl, propyl and butyl groups) andN-hydroxyethyl-N-methylmethacrylamide; an allyl compound, for example,an allyl ester (e.g., allyl acetate, allyl caproate, ally caprate, allyllaurate, allyl palmitate, allyl stearate, allyl benzoate, allylacetoacetate or ally lactate) and allyl oxyethanol; a vinyl ether, forexample, an alkyl vinyl ether (e.g., hexyl vinyl ether, octyl vinylether, decyl vinyl ether, ethylhexyl vinyl ether, methoxyethyl vinylether, ethoxyethyl vinyl ether, chloroethyl vinyl ether,1-methyl-2,2-dimethylpropyl vinyl ether, 2-ethylbutyl vinyl ether,hydroxyethyl vinyl ether, diethylene glycol vinyl ether,dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether,butylaminoethyl vinyl ether, benzyl vinyl ether or tetrahydrofurfurylvinyl ether); a vinyl ester, for example, vinyl butyrate, vinylisobutyrate, vinyl trimethylacetate, vinyl diethylacetate, vinylvalerate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate,vinyl methoxyacetate, vinyl butoxyacetate, vinyl acetoacetate, vinyllactate, vinyl β-phenylbutyrate or vinyl cyclohexylcarboxylate; adialkyl itaconate, for example, dimethyl itaconate, diethyl itaconate ordibutyl itaconate; a monoalkyl or dialkyl furnarate, for example,dibutyl fumarate; and other monomers, for example, crotonic acid,itaconic acid, maleic anhydride, maleiinide, acrylonitrile,methacrylonitrile or maleonitrile.

In addition, any addition-polymerizable unsaturated compoundscopolymerizable with monomers corresponding to the repeating unitsdescribed above may be employed.

A molar ratio of each repeating unit in the acid-decomposable resin ofcomponent (B) can be appropriately determined taking the adjustment ofmany factors including dry etching resistance of resist, standarddeveloping solution aptitude, adhesion to substrate, resist profile, andother characteristics ordinarily required for resist, for example,resolution, heat resistance and sensitivity into consideration.

Preferred embodiments of the acid-decomposable resin of component (B)according to the present invention include (1) resin (side chain type)containing a repeating unit having a partial structure including analicyclic hydrocarbon represented by formula (pI), (pII), (pIII), (pIV),(pV) or (pVI).

(2) resin (main chain type) containing a repeating unit represented byformula (II-AB). The resin of (2) includes the following resin of (3).

(3) resin (hybrid type) containing a repeating unit represented byformula (II-AB), a maleic anhydride derivative and a (meth)acrylatestructure.

A content of the repeating unit having a partial structure including analicyclic hydrocarbon represented by formula (pI), (pII), (pIII), (pIV),(pV) or (pVI) is preferably from 30 to 70% by mole, more preferably from35 to 65% by mole, and still more preferably from 40 to 60% by mole,based on the total repeating units in the acid-decomposable resin.

A content of the repeating unit represented by formula (II-AB) ispreferably from 10 to 60% by mole, more preferably from 15 to 55% bymole, and still more preferably from 20 to 50% by mole, based on thetotal repeating units in the acid-decomposable resin.

A content of the repeating unit corresponding to the additionalcopolymerization component described above can be appropriatelydetermined depending on the desired performance of resist. In general,the content is preferably 99% by mole or less, more preferably 90% bymole or less, and still more preferably 80% by mole or less, to the sumtotal of the repeating unit having a partial structure including analicyclic hydrocarbon represented by formula (pI), (pII), (pII), (pIV),(pV) or (pVI) and the repeating unit represented by formula (II-AB)

When the photosensitive composition of the present invention is used forArF exposure, it is preferred that the acid-decomposable resin does notcontain an aromatic group in order to ensure transparency of the ArFbeam.

The acid-decomposable resin for use in the present invention can besynthesized according to conventional methods, for example, radicalpolymerization. For instance, in an ordinary synthesis method, monomersare put into a reaction vessel at once or separately during thereaction, dissolved in a reaction solvent, for example, an ether, e.g.,tetrahydrofuran, 1,4-dioxane or diisopropyl ether, a ketone, e.g.,methyl ethyl ketone or methyl isobutyl ketone, an ester, e.g., ethylacetate, or a solvent dissolving the composition of the presentinvention, e.g., propylene glycol monomethyl ether acetate, if desired,to form a uniform solution, and under inert gas atmosphere, for example,nitrogen or argon, polymerization is initiated using a commerciallyavailable radical initiator (e.g., an azo initiator or a peroxide) whileheating, if desired. The initiator is further added or separately added,if desired. After the completion of the reaction, the reaction mixtureis poured into a solvent to correct the resultir. powder or solid,thereby obtaining the polymer. The concentration of reaction isordinarily not less than 20% by weight, preferably not less than 30% byweight, and more preferably not less than 40% by weight. The reactiontemperature is ordinarily from 10 to 150° C., preferably from 30 to 120°C., and more preferably from 50 to 100° C.

A weight average molecular weight of the resin of component (B) for usein the present invention is preferably form 1,000 to 200,000 measured bya GPC method and calculated in terms of polystyrene. It is not preferredthat the weight average molecular weight of the resin is less than1,000, since the degradation of heat resistance and dry etchingresistance may occur. On the other hand, when the weight averagemolecular weight of the resin is more than 200,000, undesirable results,for example, the degradation of developing property and film-formingproperty due to severe increase in viscosity may occur.

A content of the resin of component (B) in the positive photosensitivecomposition of the present invention is preferably from 40 to 99.99% byweight, and more preferably from 50 to 99.97% by weight, based on thetotal solid content of the photosensitive composition.

<<(C) Basic Compound>>

The positive photosensitive composition of the present inventioncontains a basic compound of component (C) for restraining fluctuationsin performances occurred with the passage of time from exposure to heattreatment. For instance, linewidth of resist pattern tends to changedepending on the period between the exposure and the heat treatment. Byusing the basic compound of component (C), such a change of linewidth isadvantageously restrained.

In addition, in order to improve edge roughness of pattern and torestrain development defect, a mixture of at least two basic compoundshaving different structures of component (C-1) is used according to oneembodiment of the present invention.

The mixture of two or more basic compounds having different structuresmeans a mixture of two or more basic compounds having different physicalproperties. The physical property includes for example, pKa, molecularsize, melting point, boiling point, vapor pressure and log P. The pKadenotes pKa of a conjugate acid (of the basic compound).

For instance, a mixture of basic compounds having different pka's mayinclude not only a mixture of a basic compound having a low pea and abasic compound having a high pKa but also a mixture of basic compoundshaving relatively low pKa's but slightly different pka's from each otherand a mixture of basic compounds having relatively high pKa's butslightly different pka's from each other. Specifically, a difference ofthe pea between two basic compounds is preferably not less than 0.1, andmore preferably not less than 0.5.

The pKa is a measure of basicity of a basic nitrogen atom, and it isknown that the pKa corresponds to a charge density on the nitrogen atom.The charge density of nitrogen atom can be determined by a molecularorbital calculation, for example, using MOPAC. A value of the chargedensity obtained by such a method is used as a measure of the basicity.Although various methods for the calculation are known, the calculationis ordinarily performed in the following manner. A molecular structureof the desired molecule is sterically optimized by molecular mechanicscalculation (e.g., using a MM2 parameter), and a charge density isdetermined by MOPAC (using an AM1 parameter), which is a molecularorbital calculation method taking the electron state of molecule intoconsideration. With respect to the charge density, in case of using amixture of two basic compounds, a difference of the charge densitiy onnitrogen atom between the compounds is preferably not less than 0.01,and more preferably not less than 0.02.

It is believed that the molecular size is a factor to controldiffusibility. The molecular size indicates a size of molecule and isable to be digitalized in various manners. For example, a molecularstructure of the desired molecule is sterically optimized by molecularmechanics calculation (e.g., using a MM2 parameter), and a surface areaor volume is determined by MOPAC (using an PM3 parameter), which is amolecular orbital calculation method taking the electron state ofmolecule into consideration. In general, the volume Is more preferablyused than the surface area. Since the desired diffusibility, i.e., thedesired molecular size may vary depending on the photosensitivecomposition, it is difficult to generally define an ideal size, However,it is ordinarily possible to control the diffusibility by a mixture of abasic compound having a large molecular size and a basic compound havinga small molecular size. In case of using the volume value of moleculeobtained by the above-described calculation method, a difference in themolecular size is preferably not less than 10 A³, and more preferablynot less than 15 A³.

The melting point, boiling point and vapor pressure are factors thatdominate volatility and compatibility of molecule, and they also maycontrol distribution of the molecule in a resist film, in some cases. Adifference in the melting point or boiling point is preferably not lessthan 10° C., and more preferably not less than 20° C.

The log P is known as an index representinghydrophilicity/hydrophobicity of molecule and it is an important factorrelating to compatibility in a resist film. By mixing basic compoundshaving different log P's, distribution of the compounds in the resistfilm. A difference in the log P value is preferably not less than 0.2,and more preferably not less than 0.4.

As is apparent from the description above, to mix two or more basiccompounds having different structures ordinarily results in a mixture ofcompounds having two or more different physical properties. However, amixture of compounds in which only one physical property is different issufficient for use in the present invention. Also, it should be notedthat the values of difference are not restricted to the preferred rangesdescribed above, respectively.

The basic compounds to be used preferably have a structure representedby any one of formulae (A) to (E) shown below.

In the above formula, R²⁵⁰, R²⁵¹ and R²⁵², which may be the same ordifferent, each independently represent a hydrogen atom, an alkyl grouphaving from 1 to 20 carbon atoms, an aminoalkyl group having from 1 to20 carbon atoms, a hydroxyalkyl group having from 1 to 20 carbon atomsor a substituted or unsubstituted aryl group having from 6 to 20 carbonatoms, or R²⁵⁰ and R²⁵¹ may be combined with each other to form a ring,and the alkyl chain may contain an oxygen atom, a sulfur atom or anitrogen atom,

In the above formulae, R²⁵³, R²⁵⁴, R²⁵⁵ and R²⁵⁶, which may be the sameor different, each independently represent an alkyl group having from 1to 6 carbon atoms.

Preferred examples of the basic compound include substituted orunsubitituted guanidines, substituted or unsubstituted aminopyridines,substituted or unsubstituted aminoalkylpyridines, substituted orunsubstituted aminopyrrolidines, substituted or unsubstituted indazoles,substituted or unsubstituted pyrazoles, substituted or unsubstitutedpyrazines, substituted or unsubstituted pyrimidines, substituted orunsubstituted purines, substituted or unsubstituted imidazolines,substituted or unsubstituted pyrazolines, substituted or unsubstitutedpiperazines, substituted or unsubstituted aminomorpholines, substitutedor unsubstituted aminoalkylmorpholines, mono-, di- or trialkylamines,substituted or unsubstituted anilines, substituted or unsubstitutedpiperidines and mono- or diethanolamine. Preferred examples of thesubstituent include an amino group, an aminoalkyl group, an alkylaminogroup, an aminQaryl group, an arylamino group, an alkyl group, an alkoxygroup, an acyl group, an acyloxy group, an aryl group, an aryloxy group,a nitro group, a hydroxy group and a cyano group.

Preferred specific examples of the basic compound include guanidine,1,1-dimethylguanidine, 1,1,3,3-tetramethylguanidine, 2-aminopyridlne,3-aminopyridine, 4-aminopyridine, 2-dimethylaminopyridine,4-dimethylaminopyridine, 2-diethylaminopyridine,2-(aminomethyl)pyridine, 2-amino-3-methylpyridine,2-amino-4-methylpyridine, 2-amino-5-methylpyridine,2-amino-6-methylpyridine, 3-aminoethylpyridine, 4-aminoethylpyridine,3-aminopyrrolidine, piperazine, N-(2-aminoethyl)piperazine,N-(2-aminoethyl)piperidine, 4-amino-2,2,6,6-tetramethylpiperidine,4-piperidinopiperidine, 2-iminopiperidine, 1-(2-aminoethyl)pyrrolidine,pyrazole, 3-amino-5-methylpyrazole, 5-amino-3-methyl-1-p-tolylpyrazole,pyrazine, 2-(aminomethyl)-5-methylpyrazine, pyrimidine,2,4-diaminopyrimidine, 4,6-dihydroxypyrimidine, 2-pyrazoline,3-pyrazoline, N-aminomorpholine, N-(2-aminoethyl)morpholine,1,5-diazabicyclo[4.3.0]non-5-ene, 1,8-diazabicyclo[5.4.0]undec-7-ene,2,4,5-triphenylimidazole, tri(n-butyl)amine, tri(n-octyl amine,N-phenyldiethanolamine, N-hydroxyethylpiperidine, 2,6-diisopropylanilineand N-cyclohexyl-N′-morpholinoethylthiourea. However, the basiccompounds for use in the present invention should not be limitedthereto.

More preferred compounds include substituted or unsubstitutedguanidines, substituted or unsubstituted aminopyrrolidines, substitutedor unsubstituted pyrazoles, substituted or unsubstituted pyrazolines,substituted or unsubstituted piperazines, substituted or unsubstitutedaminomorpholines, substituted or unsubstituted aminoalkylmorpholines andsubstituted or unsubstituted piperidines. Compounds having an imidazolestructure, a diazabicyclo structure, an onium hydroxide structure, anonium carboxylate structure or an aniline structure are also preferred.

The compound having an imidazole structure includes imidazole,2,4,5-triphenylimidazole and benzimidazole. The compound having adiazabicyclo structure includes 1,4-diazabipyclo[2.2.2]octane,1,5-diazabicyclo[4.3.0]non-5-ene and 1,8-diazabicyclo[5.4.0]undec-7-ene.The compound having an onium hydroxide structure includes atriarylsulfonium hydroxide, phenacyl sulfonium hydroxide and a2-oxoalkyl-containing sulfonium hydroxide, e.g., triphenylsulfoniumhydroxide, tris(t-butylphenyl)sulfonium hydroxide,bis(tert-butylphenyl)iodonium hydroxide, phenacyl thiophenium hydroxideor 2-oxopropylthiophenium hydroxide. The compound having an oniumcarboxylate structure includes a compound wherein an anion portion ofthe compound having an onium hydroxide structure is replaced by acarboxylate, e.g., acetate, adamantane-1-carboxylate or a perfluoroalkylcarboxylate. The compound having an aniline structure includes2,6-diisopropylaniline and N,N-dimethylaniline. The basic compound foruse in the present invention should not be construed as being limited tothese specific examples.

According to one embodiment of the present invention, a mixture of atleast two basic compounds having different structures of component(C-1), which are appropriately selected from the basic compoundsdescribed above, is used as the basic compound of component (C).Specifically, for example, two basic compounds having differentstructures, three basic compounds having different structures or four ormore basic compounds having different structures may be used. In case ofusing at least two basic compounds having different structures, it ispreferred that an amount of the basic compound that is used in thesmallest amount is not less than 10% by weight base on the total amountof the basic compounds used. By using at least two basic compoundshaving different structures according to the present invention, the edgeroughness of pattern is improved and the development defect isrestrained.

Specific examples of preferred combination of the basic compoundsinclude a combination of tri(n-butylamine) and diisopropylaniline, acombination of tri(n-butylamine) and N,N-dimethylpyridine, a combinationof tri(n-butylamine) and 1,8-diazabicyclo[5.4.0]undec-7-ene, acombination of tri(n-butylamine) and triphenylimidazole, a combinationof diisopropylanil-ne and N,N-dimethylpyridine, a combination ofdiisopropylaniline and 1,8-diazabicyclo[5.4.0]undec-7-ene, a combinationof diisopropylaniline and triphenylimidazole, a combination of1,5-diazabicyclo[4.3.0]non-5-ene and antipyrine, a combination ofdiisopropylaniline and dicyclohexylmethylamine, a combination ofantipyrine and tri(n-butylamine), a combination of hydroxyantipyrine andantipyrine, a combination of tetramethylammonium hydroxide anddiisopropylaniline, a combination of tetramethylammonium hydroxide andtetrabutylammonium hydroxide, a combination of tetramethylammoniumhydroxide and tri(n-butylamlne), a combination of diisopropylaniline,dicyclohexylmethylamine and tri(n-butylamine), a combination oftri(n-butylamine), 1,8-diazabicyclo[5.4.0]undec-7-ene anddiisopropylaniline, and a combination of tri(n-butylamine),1,9-diazabicyclo[5.4.0]undec-7-ene and diisopropylaniline.

The total amount of two or more basic compounds used is ordinarily from0.001 to 10% by weight, and preferably 0.01 to 5% by weight, based onthe solid content of the positive photosensitive composition. When theamount is less than 0.001% by weight, the effect of addition of basiccompounds is not obtained. When the amount exceeds 10% by weight, on theother hand, the sensitivity tends to decrease or the developabilitytends to degrade in the unexposed area.

According to another embodiment of the present invention, a basiccompound containing a substituted or unsubstituted aliphatic hydrocarbongroup having not less than 8 carbon atoms, and preferably from 8 to 19carbon atoms, of component (C-2) is used as the basic compound ofcomponent (C).

The basic compound of component (C-2) has at least one substituted orunsubstituted aliphatic hydrocarbon group having not less than 8 carbonatoms in the molecules thereof and may naturally contain two or moresubstituted or unsubstituted aliphatic hydrocarbon groups each havingnot less than 8 carbon atoms.

Examples of the substituted or unsubstituted aliphatic hydrocarbon grouphaving not less than 8 carbon atoms include n-octyl, isooctyl,tert-octyl, n-nonyl, isononyl, tert-nonyl, n-decyl, isodecyl,tert-decyl, n-undecyl, isoundecyl, tert-undecyl, n-dodecyl, isododecyltert-dodecyl, n-tridecyl, isotridecyl, tert-tridecyl, n-tetradecyl,isotetradecyl, tert-tetradecyl, n-pentadecyl, isopentadecyl,tert-pentadecyl, n-hexadecyl, isohexadecyl, tert-hexadecyl,n-heptadecyl, isoheptadecyl, tert-heptadecyl, n-octadecyl, isooctadecyl,tert-octadecyl, n-nonadecyl, isononadecyl and tert-nonadecyl groups.These groups may be substituted with a substituent. Examples of thesubstituent include an alkyl group, for example, methyl, ethyl,n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl group, an aralkylgroup, for example, benzyl group, an aryl group, for example, phenylgroup, an allyl group and a halogen atom.

The aliphatic hydrocarbon group more preferably has from 10 to 19 carbonatoms.

Examples of the basic compound containing a substituted or unsubstitutedaliphatic hydrocarbon group having not less than 8 carbon atoms are setforth below, but the present invention should not be construed as beinglimited thereto.

Octylamine, dioctylamine, trioctylamine, dioctylmethylamine, nonylamine,dinonylamine, trinonylamine, dinonylmethylamine, decylamine,didecylamine, tridecylamine, didecylmethylamine, undecylamine,diundecylamine, triundecylamine, diundecylmethylemine, dodecylamine,didodecylamine, tridodecylamine, didQdecylmethylamine, tridecylamine,ditridecylamine, tritridecylamine, ditridecylmethylamine,tetradecylamine, ditetradecylamine, tritetradecylamine,ditetradecylmethylamine, pentadecylamine, dipentadecylamine,tripentadecylanine, dipentadecylmethylamine, hexadecyl amine,dihexadecylamine, trihexadecylamine, dihexadecylmethylamine,heptadecylamine, diheptadecylamine, triheptadecylamine,diheptadecylmethylamine, octadecylamine, dioctadecylamine,trioctadecylamine, dioctadecylmethylamine, nonadecylamine,dinonadecylamine, trinonadecylamine, dinonadecylmethylamine,isoootylamine, diisooctylamine, triisooctylamine, isooctylmethylamine,isononylamine, diisononylamine, triisononylamine, diisononylmethylamine,isodecylamine, diisodecylamine, triisodecylamine, diisodecylmethylamine,isoundecylamine, diisoundecylamine, triisoundecylamine,diisoundecylmethylarine, isododecylarnine, diisododecylamine,triisododecylamine, diisododecylmethylamine, triisodecylamine,diiaotridecylamins, triisotridecylamine, diisotridecylmethylamine,isotetradecylamnine, diisotetradecylamine, triisotetradecylamine,diisotetradecylmethylamine, isopentadecylamine, diisopentadecylamine,triisopentadecylamine, diisopentadecylmethylamine, isohexadecylamine,dilsohexadecylamine, triisohexadecylamine, diisohexadecylmethylamine,isoheptadecylamine, diisqheptadecylamine, triisoheptadecylamine,diisoheptadecylmethylamine, isooctadecylamine, diisooctadecylamine,triisooctadecylamine, diisooctadecylmethylamine, isononadecylamine,diisononadecylamine, triisqnonadecylamine, diisononadecylmethylamine.

Of these compounds, tridecylamine, tetradecylamine, pentadecylamine,hexadecylamine, octadecylamine, didecylamine, methyloctadecylaamine,triisodecylamine, N,N-dimethylundecylamine, N,N-dimethyldodecylamine,tridodecylamine, methyldioctadecylamine and trioctylamine are morepreferred.

The basic compound of component (C-2) can be used in combination with aconventionally known basic compound. Examples of the basic compoundsuitable for use in combination with the basic compound of component(C-2) include a nitrogen-containing basic compound.

The nitrogen-containing basic compound used is suitably that does notsublime and deteriorate the resist performances, and includes, forexample, an organic amine, a basic ammonium salt and a basic sulfoniumsalt.

Of the nitrogen-containing basic compounds, organic amines are preferredin view of excellent image characteristics. For example, the basiccompounds described in JP-A-63-14964O, JP-A-5-249662, JP-A-5-127369,JP-A-5-289322, JP-A-5-249683, JP-A-5-289340, JP-A-5-232706,JP-A-5-252282, JP-A-6-242605, JP-A-6-242606, JP-A-6-266100,JP-A-6-266110, JP-A-6-317902, JP-A-7-120929, JP-A-7-146558,JP-A-7-319163, JP-A-7-508840, JP-A-7-333844, JP-A-7-219217,JP-A-7-92678, JP-A-7-28247, JP-A-8-22120, JP-A-8-110638, JP-A-8-123030,JP-A-9-274312, JP-A-9-166871, JP-A-9-292708, JP-A-9-325496,JP-W-7-508840 (the term “JP-W” as used herein means an “unexaminedpublished international patent application”), and U.S. Pat. Nos.5,525,453, 5,629,134 and 5,667,938 are employed.

Specific preferred examples of nitrogen-containing basic compoundlnclude 1,5-diazabicyclo[4.3.0]non-5-ene,1,8-diazabicyclo[5.4.0]undec-7-one, 1,4-diazabicyclo[2.2.2]octane,4-dimethylaminopyridine, 1-naphthylamine, piperidine,hexamethylenetetramine, an imidazole, a hydroxypyridine, a pyridine,4,4′-diaminodiphenyl ether, pyridinium p-toluenesulfonate,2,4,6-trimethylpyridinuim p-toluenesulfonate, tetramethylammoniump-coluenesulfonate, tetrabutylammonium lactate, triethylamine andtributylamine.

Of these compounds, organic amines, for example,1,5-diazabicyclo[4.3.0]non-5-ene, 1,8-diazabicyclo[5.4.0]undec-7-ene,1,4-diazabicyclo[2.2.2]octane, 4-dimethylaminopyridine, 1-naphlhylamine,piperidine, hexamethylenetetramine, an imidazole, a hydroxypyridine, apyridine, 4,4′-diaminodiphenyl ether, triethylamine and tributylamineare more preferred.

The basic compounds of component (C-2) may be used individually or as amixture of two or more thereof. The total amount of basic compoundincluding the basic compound containing a substituted or unsubstitutedaliphatic hydrocarbon group having not less than 8 carbon atoms andother basic compounds used in combination is ordinarily from 0.001 to10% by weight, and preferably 0.01 to 5% by weight, based on the solidcontent of the positive photosensitive composition. When the amount isless than 0.001% by weight, an effect of the addition of basic compoundis not obtained. When the amount exceeds 10% by weight, on the otherhand, the sensitivity tends to decrease or the developability tends todegrade in the unexposed area.

A mixing ratio of the basic compound containing a substituted orunsubstituted aliphatic hydrocarbon group having not less than 8 carbonatoms to other basic compounds used in combination is ordinarily from10/90 to 90/10 by weight, preferably from 15/85 to 85/15 by weight, andmore preferably from 20/80 to 80/20 by weight.

According to still another embodiment of the present invention, a basiccompound selected from an oxygen-containing primary aliphatic amine, anoxygen-containing secondary aliphatic amine and an oxygen-containingtertiary aliphatic amine, of component (C-3) is used as the basiccompound of component (C). The oxygen-containing primary aliphatic aminemeans a primary amine represented by R—NH₂, wherein R represents a groupcontaining an oxygen atom. Preferably, the group represented by Rincludes an ether bond. To the oxygen-containing secondary aliphaticamine and oxygen-containing tertiary aliphatic amine, the abovedescribed explanation is also applied.

Examples of the primary, secondary or tertiary oxygen-containingaliphatic amine include methoxyethoxyethylamine,bis(methoxyethoxyethyl)amine, tris[2-(methoxymethoxy)ethyl]amine,tris[2-(methoxyethoxy)ethyl]amine,tris[2-[(2-methoxyethoxy)methoxy]ethyl]amine,tris[2-(2-methoxyetboxy)ethyl]amine,tris[2-(1-methoxyethoxy)ethyl]amine,tris[2-(1-ethoxypropoxy)ethyl]amine,tris[2-[2-(2-hydroxyethoxy)ethoxy]ethyl]amine,4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8.8.8]hexacosane,4,7,13,18-tetraoxa-1,10-diazabicyclo[8.5.5]eicosane and1,4,10,13-tetraoxa-7,16-diaiabicyclooctadecane.

As the basic compound of component (C-3), for example,trismethoxymethoxyethylamine and trismethoxyethoxyethylamine are morepreferably used.

The basic compound of component (C-3) can be used in combination with aconventionally known basic compound that does not contain an oxygenatom. Examples of the basic compound suitable for use in combinationwith the basic compound of component (C-3) include a nitrogen-containingbasic compound.

The nitrogen-containing basic compound used is suitably that does notsublime and deteriorate the resist performances, and includes, forexample, an organic amine,. a basic ammonium salt and a basic sulfoniumsalt.

Of the nitrogen-containing basic compounds, organic amines are preferredin view of excellent image characteristics. For example, the basiccompounds des cribed in JP-A-63-149640, JP-A-5-249662, JP-A-5-127369,JP-A-5-289322, JP-A-5-249683, JP-A-5-289340, JP-A-5-232706,JP-A-5-252282, JP-A-6-242605, JP-A-6-242606, JP-A-6-266100,JP-A-6-266110, JP-A-6-317902, JP-A-7-120929, JP-A-7-146558,JP-A-7-319163, JP-A-7-508840, JP-A-7-333844, JP-A-7-219217,JP-A-7-92678, JP-A-7-28247, JP-A-8-22120, JP-A-8-110638, JP-A-8-123030,JP-A-9-274312, JP-A-9-166871, JP-A-9-292708, JP-A-9-325496,JP-W-7-508840 (the term “JP-W” as used herein means an “unexaminedpublished international patent application”), and U.S. Pat. Nos.5,525,453, 5,629,134 and 5,667,938 are employed.

Specific preferred examples of nitrogen-containing basic compoundinclude 1,5-diazabicyclo[4.3.0]non-5-ene,1,8-diazabicyclo[5.4.0]undec-7-ene, 1,4-diazabicyclo[2.2.2]octane,4-diniethylaminopyridine, 1-naphthylamine, piperidine,hexamethylenetetramine, an imidazole, a hydroxypyridine, a pyridine,4,4′-diaminodiphenyl ether, pyridinium p-toluenesulfonate,2,4,6-trimethylpyridinuim p-toluenesulfonate, tetramethylammoniump-toluenesulfonate, tetrabutylammonium lactate, triethylamine andtributylamine.

Of these compounds, organic amines, for example,1,5-diazabicyclo[4.3.0]non-5-ene, 1,8-diazabicyclo[5.4.0]undec-7-ene,1,4-diazabicyclo[2.2.2]octane, 4-dimethylaminopyridine, 1-naphthylamine,piperidine, hexamethylenetetramine, an imidazole, a hydroxypyridine, apyridine, 4,4′-diaminodiphenyl ether, triethylamine and tributylamineare more preferred.

The basic compounds of component (C-3) nay be used individually or as amixture of two or more thereof, The total amount of basic compoundincluding the oxygen-containing primary, secondary or tertiary aliphaticamine and other basic compounds (C′) used in combination is ordinarilyfrom 0.001 to 10% by weight, and preferably 0.01 to 5% by weight, basedon the solid content of the positive photosensitive Composition. Whenthe amount is less than 0.001% by weight, an effect of the addition ofbasic compound is not obtained. When the amount exceeds 10% by weight,on the other hand, the sensitivity tends to decrease or thedevelopability tends to degrade in the unexposed area.

A mixing ratio of the oxygen-containing primnary, secondary or tertiaryaliphatic amine to other basic. compounds (C′) used in combination isordinarily from 10/90 to 90/10 by weight, preferably from 15/85 to 85/15by weight, and more preferably from 20/80 to 80/20 by weight.

<(D) Fluorine-Base and/or Silicon-Base Surface Active Agent>

It is preferred that the positive photosensitive composition of thepresent invention contains one or more of fluorine-base and/orsilicon-base surface active agent (a fluorine atom-containing surfaceactive agent, a silicon atom-containing surface active agent and asurface active agent containing both a fluorine atom and a siliconatom).

By the addition of the surface active agent of component (D), thepositive photosensitive composition of the present invention canprovide, at high sensitivity and good resolution, resist patterns havinggood adhesion and less defect in development, when an exposure lightsource of 250 nm or less, especially 220 nm or less is used.

Specific examples of the surface active agent of component (D) includethose as described in JP-A-62-36663, JP-A-61-226746, JP-A-61-226745,JP-A-62-170950, JP-A-63-34540, JP-A-7-230165, JP-A-8-62834,JP-A-9-54432, JP-A-9-5988 and U.S. Pat. Nos. 5,405,720, 5,360,692,5,529,881, 5,296,330, 5,436,098, 5,576,143, 5,294,511 and 5,824,451.Conmmercially available surface active agents described below may alsobe used as they are. Examples of the commercially available surfaceactive agent used include fluorine-base or silicon-base surface activeagents, e.g., Eftop EF301 and EF303 (manufactured by Shin-Akita KaseiCo., Ltd.), Florad FC430 and FC431 (manufactured by Sumitomo 3M Ltd.),Megafac F171, F173, F176, F189 and R08 (manufactured by Dainippon Inkand Chemicals, Inc.), Surflon S-382, SC101, 102, 103, 104, 105 and 106(manufactured by Asahi Glass Co., Ltd.) and Troysol S-366 (manufacturedby Troy Chemical Corp.). A polysiloxane polymer KP-341 (manufactured byShin-Etau Chemical Co., Ltd.) is also used as a silicon-base surfaceactive agent.

The amount of surface active agent used is preferably from 0.0001 to 2%by weight, and more preferably from 0.001 to 1% by weight, based on thetotal amount of the positive photosensitive composition (excluding asolvent).

<(E) Organic Solvent>

The positive photosensitive composition of the present invention is usedby dissolving the above-described components in the desired organicsolvent.

Examples of the organic solvent used include ethylene dichloride,cyclohexanone, cyclopentanone, 2-heptanone, γ-butyrolactone, methylethyl ketone, ethylene glycol monomethyl ether, ethylene glycolmonoethyl ether, 2-methoxyethyl acetate, ethylene glycol monoethyl etheracetate, propylene glycol monomethyl ether, propylene glycol monomethylether acetate, toluene, ethyl acetate, methyl lactate, ethyl lactate,methyl methoxypropionate, ethyl ethoxypropionate, methyl pyruvate, ethylpyruv pte, propyl pyruvate, N,N-dimethylformamide, dimethylsulfoxide,N-methylpyrrolidone and tetrahydrofuran.

In the present invention, it is preferred to use a mixed solventcomprising a mixture of a solvent containing a hydroxy group and asolvent free from a hydroxy group. The use of such a mixed solvent makesit possible to restrain the generation of particles during storage ofthe resist solution.

Examples of the hydroxy group-containing solvent include ethyleneglycol, ethylene glycol monomethyl ether, ethylene glycol monoethylether, propylene glycol, propylene glycol monomethyl ether, propyleneglycol monoethyl ether and ethyl lactate. Of these solvents, propyleneglycol monomethyl ether and ethyl lactate are particularly preferred.

Examples of the solvent free from a hydroxy group include propyleneglycol monomethyl ether acetate, ethyl ethoxypropionate, 2-heptanone,γ-butyrolactone, cyclohexanone, butyl acetate, N-methylpyrrolidone,N,N-dimethylacetamide and dimethylsulfoxide. Of these solvents,propylene glycol monomethyl ether acetate, ethyl ethoxypropionate,2-heptanone, γ-butyrolactone, cyclohexanone and butyl acetate areparticularly preferred, and propylene glycol monomethyl ether acetate,ethyl ethoxypropionate and 2-heptanone are most preferred.

A mixing ratio (by weight) of the hydroxy group-containing solvent tothe solvent free from a hydroxy group ranges from 1/99 to 99/1,preferably from 10/90 to 90/10, and more preferably from 20/80 to 60/40.A mixed solvent containing not less than 50% by weight of the solventfree from a hydroxy group is also particularly preferred in view ofuniform coating.

<(F) Acid Decomposable Dissolution Inhibiting Compound>

It is preferred that the positive photosensitive composition of thepresent invention contains a dissolution inhibiting low molecular weightcompound of component (F) (hereinafter also referred to as an “aciddecomposable dissolution inhibiting compound”) having a group capable ofbeing decomposed by the action of an acid to increase solubility in analkali developing solution and having a molecular weight of not morethan 3,000.

In order to prevent deterioration in transmittance at 220 nm or less, analicyclic or aliphatic compound having an acid decomposable group, forexample, a cholic acid derivative having an acid decomposable group asdescribed in Proceeding of SPIE, 2724, 355 (1966) is preferred as theacid decomposable dissolution inhibiting compound of component (F).Examples of the acid decomposable group and alicyclic structure aresimilar to those described regarding the acid decomposable resin ofcomponent (B) above.

The amount of acid decomposable dissolution inhibiting compound ofcomponent (F) used is preferably from 3 to 50% by weight, and morepreferably 5 to 40% by weight, based on the solid content of the totalpoaitive photosensitive composition.

Specific examples of the acid decomposable dissolution inhibitingcompound of component (F) are set forth below, but the present inventionshould not be construed as being limited thereto.

<(G) Alkali-Soluble Resin>

The positive photosensitive composition of the present invention maycontain a resin of component (G), which does not contain anacid-decomposable group, insoluble in water but soluble in an alkalideveloping solution. By the addition of such a resin, the sensitivity ofthe photosensitive composition can be improved.

In the present invention, a novolac resin having a molecular weight offrom about 1,000 to about 20,000 and a polyhydroxystyrene derivativehaving a molecular weight of from about 3,000 to about 50,000 are usedas such a resin. Since these resins have a large absorption of light of250 nm or less, they are preferably used after being subjected topartial hydrogenation or in an amount not larger than 30t by weightbased on the total amount of resin.

Resins having a carboxy group as an alkali-solubilizing group are alsoused. The carboxy group-containing resin preferably has a monocyclic orpolycyclic alicyclic hydrocarbon group for improving dry etchingresistance. Specific examples of such a resin include a methacrylicester/(meth)acrylic acid copolymer having an alicyclic hydrocarbonstructure which does not exhibit acid decomposability and a(meth)acrylic ester resin containing an alicyclic hydrocarbon grouphaving a carboxy group at the terminal thereof.

<Other Additives>

Into the positive photosensitive composition of the present invention, adye, a plasticizer, a surface active agent other than the surface activeagent of component (D), a photosensitizer and a compound for promotingdissolution in a developing solution may be incorporated.

The dissolution promoting compound in a developing solution for use inthe present invention is a low molecular weight compound having amolecular weight of not more than 1,000 and having at least two phenolichydroxy groups or at least one carboxy group. In case of containing acarboxy group, an alicyclic or aliphatic compound is preferred becauseof the same reason as described above.

The amount of dissolution promoting compound used is preferably from 2to 50% by weight, and more preferably from 5 to 30% by weight, based onthe resin capable of being decomposed by the action of an acid toincrease solubility in an alkali developing solution of component (B).The amount exceeding 50% by weight is not preferred, because anotherproblem of the increase in development residue or the deformation ofpatterns at development may occur.

Such a phenolic compound having a molecular weight of not more than1,000 can be easily synthesized by one skilled in the art with referenceto methods as described, for example, in JP-A-4-122938, JP-A-2-28531,U.S. Pat. No. 4,916,210 and European Patent 219,294.

Specific examples of the carboxy group-containing alicyclic or aliphaticcompound include a carboxylic acid derivative having a steroidstructure, e.g., cholic acid, deoxycholic acid or lithocholic acid, anadamantanecarboxylic acid derivative, adamantanedicarboxylic acid,cyclohexanecarboxylic acid and cyclohexanedicarboxylic acid, but thepresent invention should not be construed as being limited thereto.

To the photosensitive composition of the present invention, a surfaceactive agent other than the fluorine-base and/ox silicon-base surfaceactive agent of component (D) may be added, Specific examples of suchsurface active agent include a nonionic surface active agent, forexample, a polyoxyethylene alkyl ether, e.g., polyoxyethylene laurylether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether orpolyoxyethylene oleyl ether, a polyoxyethylene alkyl aryl ether, e.g.,polyoxyethylene octyl phenol ether or polyoxyethylene nonyl phenolether, a polyoxyethylene/polyoxypropylene block copolymer, a sorbitanfatty acid ester, e.g., sorbitan monolaurate, sorbitan monopalmitate,sorbitan monostearate, sorbitan monooleate, sorbitan trioleate orsorbitan tristearate, and a polyoxyethylene sorbitan fatty acid ester,e.g., polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitanmonopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylenesorbitan trioleate or polyoxyethylene sorbitan tristearate.

The surface active agents may be used individually or in combination oftwo or more thereof.

<Method for Use>

The positive photosensitive composition of the present invention isapplied onto a desired substrate after dissolving the above componentsin a desired organic solvent, preferably in the mixed solvent asdescribed above.

Specifically, the positive photosensitive composition is applied to asubstrate (e.g., silicon/silicon dioxide coating) as used for theproduction of a precision integrated circuit element by appropriatecoating means, for example, a spinner or a coater.

After the application of positive photosensitive composition, theresulting photosensitive layer is exposed to light through a desiredmask, followed by baking and development. Thus, good resist patterns areobtained. As light for the exposure, a far ultraviolet ray havingpreferably a wavelength of 250 nm or shorter, and more preferably 220 nmor shorter is used. Specific examples thereof include a KrF excimerlaser beam (248 nm), an ArF excimer laser beam (193 nm), an F₂ excimerlaser beam (157 nm), an X-ray and an electron beam.

In the development step, a developing solution as described below isused. The developing solution for the positive photosensitivecomposition of the present invention includes an aqueous alkalinesolution containing, for example, an inorganic alkali, e.g., sodiumhydroxide, potassium hydroxide, sodium carbonate, sodium silicate,sodium metasilicate or aqueous ammonia, a primarry amine, e.g.,ethylamine or n-propylamine, a secondary amine, e.g., diethylamine ordi-n-butylamine, a tertiary amine, e.g., triethylamine ormethyldiethylamine, an alcohol amine, e.g., dimethylethanolamine ortriethanolamine, a quaternary ammonium salt, e.g., tetramethylammoniumhydroxide or tetraethylammonium hydroxide, and a cyclic amine, e.g.,pyrrole or piperidine.

A developing solution prepared by adding an appropriate amount of analcohol or a surface active agent to the aqueous alkaline solution isalso used.

The present invention is described in more detail with reference to thefollowing examples, but the present invention should not be construed asbeing limited thereto.

SYNTHESIS EXAMPLE OF RESIN Synthesis Example (1) Synthesis of Resin (1)(Side Chain Type)

2-Ethyl-2-adamantyl methacrylate and butyrolactone methacrylate in amolar ratio of 55/45 were dissolved in a mixed solvent of methyl ethylketone and tetrahydrofuran (5/5 in volume) to prepare 100 ml of asolution having a solid concentration of 20% by weight. To the solutionwas . added 2% by mole. of V-65 manufactured by Wako Pure ChemicalIndustries, Ltd., and the solution was added dropwise to 10 ml of methylethyl ketone heated at 60° C. under a nitrogen gas stream over a periodof 4 hours. After the completion of the addition, the reaction solutionwas heated for 4 hours and 1% by mole of V-65 was again added thereto,followed by stirring for 4 hours. Then, the reaction solution was cooledto room temperature and poured into 3 liters of a mixed solvent ofdistilled water and isopropyl alcohol (1/1 in volume) to crystallize,and the white powder deposited was recovered to obtain Resin (1).

A monomer unit composition ratio of the resin determined by C¹³NMR was46/54. A weight average molecular weight thereof measured by GPC methodand calculated in terms of standard polystyrene was 10,700.

Resins (2) to (18) were synthesized in a similar manner to synthesisExample (1) respectively. The monomer unit composition ratio and weightaverage molecular weight of each of ReSins (2) to (18) are shown inTable 1 below. In Table 1, Repeating Units 1, 2, 3 and 4 denote therepeating units of Resins (2) to (18) shown below in order from left toright, respectively. TABLE 1 Weight Repeating Repeating RepeatingRepeating Average Unit 1 Unit 2 Unit 3 Unit 4 Molecular Resin (mol %)(mol %) (mol %) (mol %) Weight 2 53 40 7 — 13,400 3 46 34 20 — 9,400 442 31 27 — 8,300 5 49 42 9 — 9,900 6 42 30 28 — 10,300 7 39 35 26 —8,900 8 46 22 30 2 12,900 9 42 20 32 6 11,600 10 46 42 12 — 9,200 11 3832 30 — 11,300 12 42 18 38 2 13,800 13 38 31 29 2 11,100 14 50 31 19 —11,700 15 35 6 16 43 13,200 16 50 20 20 10 11,500 17 50 40 10 — 12,30018 40 10 40 10 11,300

Structures of Resins (1) to (18) are shown below.

Synthesis Example (2) Synthesis of Resin (19) (Main Chain Type)

Into a separable flask were put tert-butyl ester of norbornenecarboxylicacid, butyrolactone ester of norbornenecarboxylic acid and maleicanhydride in a molar ratio of 40/10/50 and tetrahydrofuran in an amountnecessary for forming a solution having a reaction concentration of 60%by weight, and the solution was heated at 60° C. under a nitrogen gasstream. After the reaction temperature was stabilized, 2% by mole of aradical initiator (V-601 manufactured by Wako Pure Chemical Industries,Ltd.) was added to initiate a reaction. After heating for 12 hours, thereaction mixture was diluted twice with tetrahydrofuran and poured intoa solvent mixture of hexane and isopropyl alcohol (1/1 in volume) todeposit white powder. The powder was collected by filtration and driedto obtain Resin (19).

Resin (19) was subjected to molecular weight analysis by a GPC methodand it was found that a weight average molecular weight thereofcalculated in terms of polystyrene was 8,300. A molar ratio of repeatingunits corresponding to the tert-butyl ester of norbornenecarboxylicacid, butyrolactone ester of norbornenecarboxylic acid and maleicanhydride determined from an NMR spectrum was 42/8/50.

Resins (20) to (30) were synthesized in a similar manner to SynthesisExample (2) respectively. The monomer unit composition ratio and weightaverage molecular weight of each of Resins (20) to (30) are shown inTable 2 below. In Table 2, Alicyclic Olefin Units 1, 2 and 3 denotes therepeating units of Resins (20) to (30) shown below in order from left toright, respectively. TABLE 2 Alicyclic Alicyclic Alicyclic Maleic WeightOlefin Olefin Olefin Anhydride Average Unit 1 Unit 2 Unit 3 UnitMolecular Resin (mol %) (mol %) (mol %) (mol %) Weight 20 35 15 — 508,200 21 20 30 — 50 8,600 22 36 14 — 50 9,100 23 31 19 — 50 7,900 24 355 10 50 8,300 25 33 17 — 50 8,500 26 38 12 — 50 8,900 27 31 6 13 508,100 28 33 7 10 50 9,100 29 40 10 — 50 9,300 30 34 16 — 50 8,800

Structures of Resins (19) to (30) are shown below.

Synthesis Example (3) Synthesis of Resin (31) (Hybrid Type)

Into a reaction vessel were put norbornene, maleic anhydride, tert-butylacrylate and 2-methylcyclohexyl-2-propyl acrylate in a molar ratio of35/35/20/10 and dissolved in tetrahydrofuran to form a solution having asolid content of 60% by weight, and the solution was heated at 65° C.under a nitrogen gas stream. After the reaction temperature wasstabilized, 1% by mole of a radical initiator (V-601 manufactured byWako Pure Chemical Industries, Ltd.) was added to initiate a reaction.After heating for 8 hours, the reaction mixture was diluted twice withtetrahydrofuran and poured into hexane of five times in volume todeposit white powder. The powder was collected by filtration anddissolved in methyl ethyl ketone and the solution was poured into amixed solvent of hexane and tert-butyl methyl ether (1/1 in volume) offive times in volume to reprecipitate. The white powder deposited wascollected by filtration and dried to obtain Resin (31).

Resin (31) was subjected to molecular weight analysis by a GPC methodand it was found that a weight average molecular weight thereofcalculated in terms of polystyrene was 12,100. A molar ratio ofrepeating units corresponding to the nqrbornene, maleic anhydride,tert-butyl acrylate and 2-methylcyclohexyl-2-propyl acrylate determinedfrom an NMR spectrum was 32/39/19/10.

Resins (32) to (44) were synthesized in a similar manner to SynthesisExample (3) respectively. The monomer unit composition ratio and weightaverage molecular weight of each of Resins (32) to (44) are shown inTable 3. below. in Table 3, Norbornene Unit, Acid Anhydride Unit and(Meth)acrylate Unit denotes the repeating units of Resins (32) to (44)shown below in order from left to right, respectively. TABLE 3 AcidWeight Norbornene Anhydride (Meth)acrylate Average Unit Unit UnitMolecular Resin (mol %) (mol %) (mol %) Weight 32 20/15 40 15/10 11,90033 32 37 20/8/3 10,500 34 16 21 36/27 13,900 35 15 22 34/29 12,300 36 1720 33/30 12,400 37 18 24 32/26 13,000 38 15 19 36/30 12,700 39 15 2029/10/26 13,100 40 17 21 31/31 12,800 41 18 17/3 30/32 13,300 42 16 1931/12/11/11 12,600 43 20 22 58 14,700 44 23 28 35/14 13,300

Structures of Resins (31) to (44) are shown below.

Synthesis Example (4) Synthesis of Resin (45) (Hybrid Type)

Into a reaction vessel were put tert-butyl ester of norbornenecarboxylicacid, maleic anhydride, 2-methyl-2-adamantyl acrylate andnorbornenelactone acrylate in a molar ratio of 20/20135/25 and dissolvedin a mixed solvent of methyl ethyl ketone and tetrahydrofuran (1/1 involume) to form a solution having a solid content of 60% by weight, andthe solution was heated at 65° C. under a nitrogen gas stream. After thereaction temperature was stabilized, 3% by mole of a radical initiator(V-601 manufactured by Wako Pure Chemical Industries, Ltd.) was added toinitiate a reaction. After heating for 12 hours, the reaction mixturewas poured into hexane of five times in volume to deposit white powder.The powder was collected by filtration and dissolved in a mixed solventof methyl ethyl ketone and tetrahydrofuran (1/1 in volume), the solutionwas poured into a solvent mixture of hexane and methyl tert-butyl ether(1/1 in volume) of five times in volume to deposit white powder, and thepowder was collected by filtration. This procedure was repeated onceagain and the powder deposited was dried to obtain Resin (45).

Resin (45) was subjected to molecular weight analysis (RI analysis) by aGPC method and it was found that a weight average molecular weightthereof calculated in terms of polystyrene was 11,600. An amount of theremaining monomer was 0.4%. A molar ratio of repeating unitscorresponding to the tert-butyl ester of norbornenecarboxyliq acid,maleic anhydride, 2-methyl-2-adamantyl acrylate and norbornenelactoneacrylate determined from an NMR spectrum was 18/23/34/25.

Resins (46) to (69) were synthesized in a similar manner to SynthesisExample (4) respectively, The monomer unit Composition ratio and weightaverage molecular weight of each of Resins (46) to (69) are shown inTable 4 below, In Table 4, Alicyclic Olefin Unit, Monomer Unit ofFormula (VIII) and Acrylic Monomer Unit denotes the repeating units ofResins (46) to (69) shown below in order from left to right,respectively. TABLE 4 Monomer of Formula (VIII) Alicyclic (Acid AcrylicMonomer Weight Average Olefin Unit Anhydride) Unit Molecular Resin (mol%) (mol %) (mol %) Weight 46 24 29 31/16 12,300 47 21 28 32/29 11,100 4822 27 28/23 11,300 49 27 31 24/18 10,700 50 32 38 20/10 9,700 51 31 3521/13 9,200 52 29 35 20/16 8,900 53 35 39 23/3  8,700 54 28 36 22/1410,600 55 28/8  44 20 9,100 56 30/6  42 22 7,700 57 46 47/3  4 6,300 5837/6  48  9 6,800 59 34/10 51  5 7,400 60 41 43 10/6  6,700 61 39 4211/8  8,800 62 36 42 10/12 9,300 63 39 43 14/4  9,800 64 38 42 15/5 9,300 65 24 27 25/24 12,600 66 19 24 40/17 9,500 67 29 32 34/5  10,40068 20 25 26/5/24 13,400 69 16 24 32/24/4 12,700

Structures of Resins (45) to (69) are shown below.

Examples 1 to 76 and Comparative Examples 1 to 4

<Preparation of Photosensitive Composition>

In each of Examples 1 to 76 and Comparative Examples 1 to 4, thecomponents as shown in Tables 5 to 8 below were dissolved to prepare asolution having a solid concentration of 12% by weight. The resultingsolution was filtered through a Teflon filter having a pore size of 0.1μm, whereby a positive photosensitive composition was prepared.

The photosensitive composition was evaluated by the mehods describedbelow. The results obtained are shown in Tables 9 to 11 below. TABLE 5Surface Acid Other Basic Active Solvent Resin Generator AdditiveCompound Agent (weight Example (10 g) (g) (g) (0.03 g) (0.03 g) ratio) 1(1)  Z2 (0.045) — 1/2 = 1/1 W-1 A1/B1 = 95/5 2 (2)  Z2 (0.045) — 1/3 =1/1 W-1 A1 = 100 3 (3)  Z3 (0.045) — 2/7 = 1/1 W-2 A1/B1 = 90/10 4 (4) Z8 (0.047) — 3/8 = 1/1 W-2 A3/B2 = 80/20 5 (5)  Z5 (0.043) — 4/8 = 1/1W-3 A2/B1 = 90/10 6 (6) Z19 (0.090) — 4/9 = 1/1 W-3 A4/B1 = 90/10 7 (7)Z20 (0.090) — 3/10 = 1/1 W-4 A1/B1 = 50/50 8 (8) Z21 (0.095) — 9/10 =1/1 W-4 A1/B1 = 90/10 9 (9) Z21 (0.098) LCB (1) 1/3/9 = 1/1/1 W-1 A5/B2= 90/10 10 (10) Z34 (0.045) — 2/4/8 = 1/1/1 W-1 A1/B1 = 95/5 11 (11) Z31(0.075) — 1/4/10 = 1/1/1 W-2 A/B1 = 90/10 12 (12) Z38 (0.090) — 2/5 =1/1 W-2 A1/B1 = 95/5 13 (13)  Z2 (0.030) — 3/6 = 1/1 W-3 A1/B1 = 95/5Z31 (0.050) 14 (14)  Z3 (0.030) — 1/7 = 1/1 W-3 A1/B1 = 95/5 Z38 (0.050)15 (15)  Z2 (0.030) LCB (1) 2/9 = 1/1 W-4 A1/B1 = 80/20 Z38 (0.045) 16(16) Z31 (0.095) — 1/3 = 1/1 W-4 A1/B1 = 80/20 17 (17) Z40 (0.090) — 3/7= 1/1 W-4 A1/B1 = 95/5 18 (18) Z36 (0.090) — 4/6 = 1/1 W-4 A1/B1 = 95/519 (19) Z19 (0.060) — 5/8 = 1/1 W-4 A1/B1 = 95/5 Z14 (0.030) 20 (20)  Z2(0.045) — 6/7 = 1/1 W-4 A1/B1 = 95/5

TABLE 6 Surface Acid Other Basic Active Solvent Resin Generator AdditiveCompound Agent (weight Example (10 g) (g) (g) (0.03 g) (0.03 g) ratio)21 (21)  Z2 (0.045) — 4/8 = 1/1 W-1 A1/B1 = 95/5 22 (22) Z19 (0.090) —3/7/9 = 1/1/1 W-1 A1/B1 = 80/20 23 (23)  Z2 (0.040) — 4/8 = 1/1 W-2A1/B1 = 90/10 Z11 (0.040) 24 (24) Z13 (0.043) — 2/7 = 1/1 W-2 A3/B2 =80/20 25 (25) Z13 (0.045) — 5/6 = 1/1 W-3 A2/B1 = 90/10 Z12 (0.020) 26(26)  Z8 (0.045) — 2/4/9 = 1/1/1 W-3 A4/B1 = 90/10 27 (27)  Z8 (0.045) —3/8 = 1/1 W-4 A1/B1 = 50/50 28 (28)  Z8 (0.045) — 4/7 = 1/1 W-4 A1/B1 =90/10 Z12 (0.020) 29 (29) Z30 (0.060) LCB (1) 4/7 = 1/1 W-1 A5/B2 =90/10 Z26 (0.020) 30 (30) Z30 (0.070) — 2/3/8 = 1/1/1 W-1 A1/B1 = 95/5Z27 (0.020) 31 (31)  Z8 (0.040) — 3/4/5 = 1/1/1 W-2 A1/B1 = 90/10 Z29(0.030) 32 (32) Z33 (0.040) — 6/8 = 1/1 W-2 A1/B1 = 95/5 33 (33) Z34(0.040) — 3/4/8 = 1/1/1 W-3 A1/B1 = 95/5 34 (34) Z33 (0.040) — 2/5/9 =1/1/1 W-3 A1/B2 = 95/5 Z30 (0.020) 35 (35) Z33 (0.040) — 3/6/9 = 1/1/1W-4 A1/B1 = 80/20 Z30 (0.020) 36 (36) Z34 (0.040) — 2/5/8 = 1/1/1 W-4A1/B1 = 80/20 Z36 (0.080) 37 (37) Z40 (0.060) — 1/3/7 = 1/1/1 W-4 A1/B1= 95/5 Z34 (0.020) 38 (38) Z38 (0.040) — 6/8/10 = 1/1/1 W-4 A1/B1 = 95/5Z33 (0.040) 39 (39) Z23 (0.050) — 3/7/9 = 1/1/1 W-4 A1/B1 = 95/5 Z30(0.030) 40 (40)  Z2 (0.045) LCB (1) 2/8 = 1/1 W-4 A1/B1 = 95/5  Z7(0.020)

TABLE 7 Surface Acid Other Basic Active Solvent Resin Generator AdditiveCompound Agent (weight Example (10 g) (g) (g) (0.03 g) (0.03 g) ratio)41 (41)  Z9 (0.045) — 1/4/7 = 1/1/1 W-1 A1/B1 = 95/5 42 (42) Z10 (0.045)— 2/3/8 = 1/1/1 W-1 A1/B1 = 80/20 43 (43)  Z2 (0.035) — 5/6/9 = 1/1/1W-2 A1/B1 = 90/10  Z1 (0.010) 44 (44)  Z6 (0.040) — 4/7 = 1/1 W-2 A3/B2= 80/20 45 (45)  Z6 (0.030) — 3/8 = 1/1 W-3 A2/B1 = 90/10  Z1 (0.015) 46(46) Z16 (0.040) — 2/9 = 1/1 W-3 A4/B1 = 90/10 47 (47)  Z2 (0.045) —2/8/9 = 1/1/1 W-4 A1/B1 = 50/50 Z18 (0.010) 48 (48) Z19 (0.040) — 3/7/9= 1/1/1 W-4 A1/B1 = 90/10 Z20 (0.040) 49 (49)  Z8 (0.045) — 4/8 = 1/1W-1 A5/B2 = 90/10 Z12 (0.020) 50 (50) Z33 (0.040) — 5/7 = 1/1 W-1 A1/B1= 95/5 51 (51) Z30 (0.060) — 2/3/8 = 1/1/1 W-2 A1/B1 = 90/10 Z36 (0.020)52 (52) Z33 (0.040) — 4/5/9 = 1/1/1 W-2 A1/B1 = 95/5 53 (53) Z33 (0.040)— 3/6/8 = 1/1/1 W-3 A1/B1 = 95/5 Z30 (0.020) 54 (54) Z40 (0.060) — 2/5/7= 1/1/1 W-3 A1/B1 = 95/5 Z34 (0.020) 55 (55) Z23 (0.050) — 3/4/8 = 1/1/1W-4 A1/B1 = 80/20 Z30 (0.030) 56 (56)  Z9 (0.045) — 5/7/9 = 1/1/1 W-4A1/B1 = 80/20 57 (57)  Z9 (0.045) — 2/4/8 = 1/1/1 W-4 A1/B1 = 95/5 58(58)  Z2 (0.035) — 3/5/9 = 1/1/1 W-4 A1/B1 = 95/5  Z1 (0.010) 59 (59) Z6 (0.050) — 2/6/7 = 1/1/1 W-4 A1/B1 = 95/5 60 (60) Z16 (0.040) — 5/9 =1/1 W-4 A1/B2 = 95/5

TABLE 8 Surface Acid Other Basic Active Solvent Resin Generator AdditiveCompound Agent (weight Example (10 g) (g) (g) (0.03 g) (0.03 g) ratio)61 (61)  Z2 (0.045) — 4/10 = 1/1 W-1 A1/B1 = 95/5  Z8 (0.010) 62 (62)Z33 (0.040) — 1/10 = 1/1 W-1 A1/B1 = 80/20 63 (63)  Z8 (0.045) — 1/4/10= 1/1/1 W-2 A1/B1 = 90/10 Z12 (0.020) 64 (64) Z16 (0.040) — 3/7 = 1/1W-2 A3/B2 = 80/20 65 (65)  Z2 (0.045) — 2/5/8 = 1/1/1 W-3 A2/B1 = 90/10Z20 (0.020) 66 (66)  Z8 (0.045) — 3/6 = 1/1 W-3 A4/B1 = 90/10 Z12(0.020) 67 (67) Z23 (0.050) — 1/2/9 = 1/1/1 W-1 A1/B1 = 90/10 Z30(0.030) 68 (68) Z33 (0.040) — 2/3/5 = 1/1/1 W-1 A1/B1 = 95/5 69 (69) Z30(0.040) — 4/6/8 = 1/1/1 W-4 A1/B1 = 90/10 Z26 (0.020) 70 (16)  Z9(0.045) — 5/9 = 1/1 W-4 A1/B1 = 80/20 71 (16) Z31 (0.095) — 3/6/10 =1/1/1 W-3 A2/B1 = 90/10 72 (16) Z40 (0.090) — 1/6 = 1/1 W-2 A1/B1 = 95/573 (16) Z36 (0.090) — 1/6/10 = 1/1/1 W-1 A1/B1 = 95/5 74 (17)  Z2(0.045) — 4/3/1 = 1/1/1 W-3 A1/B1 = 90/10 Z12 (0.020) 75 (17) Z14(0.045) — 8/1 = 1/1 W-2 A1/B1 = 90/10 Z22 (0.020) 76 (17)  Z2 (0.045) —9/1/3 = 1/1/1 W-1 A1/B1 = 80/20 Z12 (0.020) Comparative  (1)  Z6 (0.045)—  2 W-1 A1/B1 = 95/5 Example 1 Comparative (13)  Z6 (0.040) —  1 W-1A1/B1 = 95/5 Example 2 Z36 (0.080) Comparative (16)  Z6 (0.040) —  3 W-1A1/B1 = 95/5 Example 3 Z39 (0.080) Comparative (17)  Z6 (0.045) — 10 W-1A1/B1 = 95/5 Example 4

The abbreviations used in Tables 5 to 3 are described below.

LCB: t-Butyl Lithocholate

The abbreviations of the basic compounds are as follows. The ratio ofbasic compounds shown in Tables 5 to 8 is indicated by a weight ratio,and the total amount of the basic compounds is 0.03 g.

-   1: Tri(n-butyl)amine-   2: Triphenylimidazole-   3: Diisopropylaniline-   4: Antipyrine-   5: Hydroxyantipyrine-   6: 1,8-Diazabicyclo[5.4.0]undec-5-ene-   7: 1,5-Diazabicyclo[4.3.0]non-5-ene-   8: Tetramethylammonium hydroxide-   9: Tetrabutylammonium hydroxide-   10: Dicyclohexylmethylamine

The abbreviations of the surface active agents are as follows.

-   W-1: Megafax F176 (manufactured by Dainippon Ink and Chemicals,    Inc.) (fluorine-base)-   W-2: Megafac R08 (manufactured by Dainippon Ink and Chemicals, Inc.)    (fluorine- and silicon-base)-   W-3: Polysiloxane Polymer KP-341 (manufactured by Shin-Etsu Chemical    Co., Ltd.) (silicon-base)-   W-4: Troysol S-366 (manufactured by Troy Chemical Co., Ltd.)

The abbreviations of the solvents are as follows. The ratio of solventsin case of using two or more thereof shown in Tables 5 to 8 is indicatedby a weight ratio.

-   A1: Propylene glycol methyl ether acetate-   A2: 2-Heptanone-   A3: Ethyl ethoxypropionate-   A4: γ-Butyrolactone-   A5: Cyclohexanone-   B1: Propylene glycol methyl ether-   B2: Ethyl lactate

The basic compounds used in Examples 1 to 76 have the physicalproperties shown in Table A below. By comparing the basic compounds usedin each example with the physical properties thereof shown in Table A,it can be seen that two basic compounds having different physicalproperties are mixed. It is also recognized that a difference in atleast one physical property is sufficient for the mixture of basiccompounds according to the present invention.

The value of pKa, which is one of indexes of the physical properties, isnot described in Table A, since it changes depending on a solvent usedfor measurement. The charge density is shown in Table A instead of thepKa. In case of an amine, the charge on the nitrogen atom thereof issubstantially corresponds to the pKa, and in case of a compound having ahydroxy ion (e.g., Basic Compounds 8 and 9), the charge on the oxygenatom of OH⁻ corresponds to the pKa. TABLE A Charge Charge Boiling ChargeDensity Density Melting Point Basic Volume^(a)) Log Density 2 on on O ofPoint (° C. or Compound (A³) P^(b)) on N^(c)) N^(d)) OH^(−e)) (° C.) °C./mmHg) 1 158.60 3.779 −0.273 — — −70 216 2 187.33 5.480 −0.188 −0.130— 275-277 — 3 134.92 3.651 −0.332 — — −45 257 4 88.19 —^(f)) −0.286−0.050 — 111-114 — 5 122.19 —^(f)) −0.192 −0.087 — 184-186 — 6 111.861.680 −0.304 −0.251 — — 80-83/ 0.6 mm 7 87.46 0.816 −0.285 −0.226 — —95-98/ 7.5 mm 8 71.47 —^(f)) 0.200 — −0.457 — — 9 180.13 —^(f)) 0.209 —−0.446 — — 10 156.94 3.327 −0.275 — — 194-196 265Notes:^(a))determined by optimizing molecular mechanically an initialstructure using a MM2 parameter, optimizing an secondary structure usinga PM3 parameter, and calculating a volume by MOPAC according to a CAChesystem.^(b))determined by an ordinary atomic calculation method.^(c))determined by optimizing molecular mechanically an initialstructure using a MM2 parameter, optimizing an secondary structure usingan AM1 parameter, and calculating a charge density by MOPAC according toa CAChe system.^(d))determined in the same manner as in c), only in case of a compoundhaving two nitrogen atoms in its molecule.^(e))determined in the same manner as in c), only in case of a compoundwherein the basicity reults from OH⁻.^(f))unable to be determined, because the compound contains an atom thatis not included in a parameter of the calculation method of log P used.<Evaluation of Pattern>

On a silicon substrate which had been subjected to ahexamethyldisilazane treatment was uniformly coated a reflectionpreventing film (DUV-42 manufactured by Brewer Science, Inc.) at athickness of 600 angstroms by a spin coater, dried at 100° C. for 90seconds on a hot plate, and further dried by heating at 190° C. for 240seconds. Thereafter, each of the photosensitive compositions describedabove was coated thereon by a spin ooater and dried at 120° C. for 90seconds to form a resist film having a thickness of 0.30 μm. The resistfilm was subjected to exposure using an ArF excimer laser stepper(manufacture by ISI Co., Ltd.; NA=0.6) through a mask and heated at 120°C. for 90 seconds on a hot plate immediately after the exposure. Thenthe resist film was developed with a 2.38% by weight aqueoustetramethylammonium hydroxide solution at 23° C. for 60 seconds, rinsedwith pure water for 30 seconds, and dried to form an L/S pattern of 0.15μm.

(1) Evaluation of Fluctuation in Linewidth

An LIS pattern was formed in the same manner as above except forconducting the heat treatment one hour after the exposure in place ofimmediately after the exposure. The linewidth of the pattern wasmeasured using a critical dimension scanning electron microscope, anddifference between the line width thus obtained and 0.15 Jm wasdetermined. As the difference is smaller, the fluctuation of linewidthwith the passage of time between the exposure and the heat treatment isless.

(2) Evaluation of Edge Roughness

The evaluation of edge roughness was conducted by measuring edgeroughness of isolated pattern using a critical dimension scanningelectron microscope (CD-SEM). Specifically, a distance from the standardline where the edge should be present to the edge of the line patternwas measured in 50 points in the area of a length of 5 μm of the linepattern. using a CD-SEM (S-8840, manufactured by Hitachi, Ltd.),standard deviation was determined and 3σ was calculated. As the value issmaller, the better quality is obtained.

(3) Evaluation of Development Defect

With the resist pattern obtained above, a number of development defectoccurred was measured by a device (KLA-2112 manufactured by KLA-TencorCorp.). The primary datum was designated as the number of developmentdefect. TABLE 9 Fluctuation Edge in Linewidth Roughness DevelopmentExample (μm) (nm) Defect 1 0.002 4 3 2 0.002 3 2 3 0.003 4 3 4 0.002 5 15 0.002 4 2 6 0.003 6 1 7 0.002 4 2 8 0.002 5 3 9 0.002 6 1 10 0.002 5 211 0.003 6 1 12 0.002 4 3 13 0.003 6 1 14 0.003 3 2 15 0.003 4 3 160.003 6 0 17 0.003 5 1 18 0.003 4 0 19 0.002 6 2 20 0.002 4 1 21 0.002 50 22 0.003 4 0 23 0.002 6 1 24 0.003 5 2 25 0.002 5 1

TABLE 10 Fluctuation in Linewidth Edge Roughness Example (μm) (nm)Development Defect 26 0.003 4 1 27 0.002 5 2 28 0.002 4 1 29 0.003 6 030 0.003 4 0 31 0.002 5 1 32 0.003 4 1 33 0.002 6 1 34 0.002 4 3 350.003 4 1 36 0.002 5 2 37 0.003 6 1 38 0.002 5 1 39 0.003 5 2 40 0.003 51 41 0.002 4 2 42 0.003 4 1 43 0.002 6 1 44 0.003 4 0 45 0.002 6 0 460.003 4 1 47 0.002 4 2 48 0.002 5 2 49 0.002 4 1 50 0.002 4 2

TABLE 11 Fluctuation Edge in Linewidth Roughness Development Example(μm) (nm) Defect 51 0.002 4 2 52 0.003 6 1 53 0.003 4 0 54 0.003 5 1 550.002 4 1 56 0.003 4 2 57 0.003 6 0 58 0.002 4 1 59 0.002 6 0 60 0.002 51 61 0.003 4 2 62 0.002 6 2 63 0.003 4 0 64 0.002 4 0 65 0.002 4 1 660.003 5 1 67 0.002 5 1 68 0.003 6 2 69 0.002 4 2 70 0.002 4 0 71 0.002 51 72 0.002 6 2 73 0.003 6 1 74 0.003 5 0 75 0.002 4 2 76 0.002 6 2Comparative 0.01 19 39 Example 1 Comparative 0.01 16 37 Example 2Comparative 0.01 18 43 Example 3 Comparative 0.01 19 42 Example 4

From the results shown in Tables 9 to 11, it can be seen that thephotosensitive compositions of Examples 1 to 76 exhibit the excellentedge roughness and restrained development defect as well as the smallfluctuation in linewidth. On the contrary, the photosensitivecompositions of Comparative Examples 1 to 4 are inferior in the edgeroughness and development defect as compared with the photosensitivecompositions of Examples.

Examples 101 to 176 and Comparative Examples 101 to 104

<Preparation of Photosensitive Composition>

In each of Examples 101 to 176 and Comparative Examples 101 to 104, thecomponents as shown in Tables 105 to 107 below were dissolved to preparea solution having a solid concentration of 12% by weight. The resultingsolution was filtered through a Teflon filter having a pore size of 0.1μm, whereby a positive photosensitive composition was prepared.

The photosensitive composition was evaluated by.the methods describedbelow. The results obtained are shown in Tables 108 to 110 below. TABLE105 Surface Acid Basic Active Solvent Resin Generator Compound Agent(weight Example (10 g) (mg) (0.03 g) (0.03 g) ratio) 101 (1)  Z2 (45) C1W-1 A1/B1 = 95/5 102 (2)  Z2 (45) C1 W-1 A1 = 100 103 (3)  Z3 (45) C2W-2 A1/B1 = 90/10 104 (4)  Z8 (47) C3 W-2 A3/B2 = 90/20 105 (5)  Z5 (43)C4 W-3 A2/B1 = 90/10 106 (6) Z19 (90) C5 W-3 A4/B1 = 90/10 107 (7) Z20(90) C13 W-4 A1/B1 = 50/50 108 (8) Z21 (95) C7 W-4 A1/B1 = 90/10 109 (9)Z21 (98) C8 W-1 A5/B2 = 90/10 110 (10) Z34 (45) C9 W-1 A1/B1 = 95/5 111(11) Z31 (75) C10 W-2 A1/B1 = 90/10 112 (12) Z38 (90) C8 W-2 A1/B1 =95/5 113 (13)  Z2 (30) C7 W-3 A1/B1 = 95/5 Z31 (50) 114 (14)  Z3 (30)C7/2 = 1/1 W-3 A1/B1 = 95/5 Z38 (50) 115 (15)  Z2 (30) C9 W-4 A1/B1 =80/20 Z38 (45) 116 (16) Z31 (95) C11 W-4 A1/B1 = 80/20 117 (17) Z40 (90)C12 W-4 A1/B1 = 95/5 118 (18) Z36 (90) C11 W-4 A1/B1 = 95/5 119 (19) Z19(60) C8 W-4 A1/B1 = 95/5 Z14 (30) 120 (20)  Z2 (45) C7/3 = 1/1 W-4 A1/B1= 95/5 121 (21)  Z2 (45) C7/3 = 1/1 W-1 A1/B1 = 95/5 122 (22) Z19 (90)C12 W-1 A1/B1 = 80/20 123 (23)  Z2 (40) C6 W-2 A1/B1 = 90/10 Z11 (40)124 (24) Z13 (43) C8 W-2 A3/B2 = 80/20 125 (25) Z13 (45) C9 W-3 A2/B1 =90/10 Z12 (20)

TABLE 106 Surface Acid Basic Active Solvent Resin Generator CompoundAgent (weight Example (10 g) (mg) (0.03 g) (0.03 g) ratio) 126 (26)  Z8(45) C1 W-3 A4/B1 = 90/10 127 (27)  Z8 (45) C1 W-4 A1/B1 = 50/50 128(28)  Z8 (45) C1/1 = 1/1 W-4 A1/B1 = 90/10 Z12 (20) 129 (29) Z30 (60)C2/4 = 1/1 W-1 A5/B2 = 90/10 Z26 (20) 130 (30) Z30 (70) C3 W-1 A1/B1 =95/5 Z27 (20) 131 (31)  Z8 (40) C4 W-2 A1/B1 = 90/10 Z29 (30) 132 (32)Z33 (40) C3 W-2 A1/B1 = 95/5 133 (33) Z34 (40) C2 W-3 A1/B1 = 95/5 134(34) Z33 (40) C5 W-3 A1/B2 = 95/5 Z30 (20) 135 (35) Z33 (40) C1 W-4A1/B1 = 80/20 Z30 (20) 136 (36) Z34 (40) C1/3 = 1/1 W-4 A1/B1 = 80/20Z36 (80) 137 (37) Z40 (60) C2 W-4 A1/B1 = 95/5 Z34 (20) 138 (38) Z38(40) C4/4 = 1/1 W-4 A1/B1 = 95/5 Z33 (40) 139 (39) Z23 (50) C3 W-4 A1/B1= 95/5 Z30 (30) 140 (40)  Z2 (45) C2/5 = 1/1 W-4 A1/B1 = 95/5  Z7 (20)141 (41)  Z9 (45) C4 W-1 A1/B1 = 95/5 142 (42) Z10 (45) C1 W-1 A1/B1 =80/20 143 (43)  Z2 (35) C2 W-2 A1/B1 = 90/10  Z1 (10) 144 (44)  Z6 (40)C1 W-2 A3/B2 = 80/20 145 (45)  Z6 (30) C3 W-3 A2/B1 = 90/10  Z1 (15) 146(46) Z16 (40) C4 W-3 A4/B1 = 90/10 147 (47)  Z2 (45) C5 W-4 A1/B1 =50/50 Z18 (10) 148 (48) Z19 (40) C7 W-4 A1/B1 = 90/10 Z20 (40) 149 (49) Z8 (45) C1 W-1 A5/B2 = 90/10 Z12 (20) 150 (50) Z33 (40) C2 W-1 A1/B1 =95/5

TABLE 107 Surface Resin Acid Basic Active Solvent (10 Generator CompoundAgent (weight Example g) (mg) (0.03 g) (0.03 g) ratio) 151 (51) Z30 (60)C13 W-2 A1/B1 = 90/10 Z26 (20) 152 (52) Z33 (40) C11 W-2 A1/B1 = 95/5153 (53) Z33 (40) C12 W-3 A1/B1 = 95/5 Z30 (20) 154 (54) Z40 (60) C9 W-3A1/B1 = 95/5 Z34 (20) 155 (55) Z23 (30) C2/3 = 1/1 W-4 A1/B1 = 80/20 Z30(30) 156 (56)  Z9 (45) C2/5 = 1/1 W-4 A1/B1 = 80/20 157 (57)  Z9 (45) C8W-4 A1/B1 = 95/5 158 (58)  Z2 (35) C6 W-4 A1/B1 = 95/5  Z1 (10) 159 (59) Z6 (50) C4 W-4 A1/B1 = 95/5 160 (60) Z16 (40) C2 W-4 A1/B1 = 95/5 161(61)  Z2 (45) C1 W-1 A1/B1 = 95/5 Z18 (10) 162 (62) Z33 (40) C3/3 = 1/1W-1 A1/B1 = 90/20 163 (63)  Z8 (45) C4 W-2 A1/B1 = 90/10 Z12 (20) 164(64) Z16 (40) C1 W-2 A3/B2 = 80/20 165 (65)  Z2 (45) C2 W-3 A2/B1 =90/10 Z20 (20) 166 (66)  Z8 (45) C3 W-3 A4/B1 = 90/10 Z12 (20) 167 (67)Z23 (50) C1/3 = 1/1 W-1 A1/B1 = 90/10 Z30 (30) 168 (68) Z33 (40) C11/1 =1/1 W-1 A1/B1 = 95/5 169 (69) Z30 (40) C5/2 = 1/1 W-4 A1/B1 = 90/10 Z26(20) 170 (16)  Z9 (45) C11/1 = 1/1 W-4 A1/B1 = 80/20 171 (16) Z31 (95)C12/3 = 1/1 W-3 A2/B1 = 90/10 172 (16) Z40 (90) C10 W-2 A1/B1 = 95/5 173(16) Z36 (90) C9/3 = 1/1 W-1 A1/B1 = 95/5 174 (17)  Z2 (45) C11/3 = 1/1W-3 A1/B1 = 90/10 Z12 (20) 175 (17)  Z2 (45) C7/6 = 1/1 W-2 A1/B1 =90/10 Z12 (20) 176 (17) Z14 (45) C11/6 = 1/1 W-1 A1/B1 = 80/20 Z22 (20)Comparative (1)  Z6 (45) 3 W-1 A1/B1 = 95/5 Example 101 Comparative (13) Z6 (40) 3 W-1 A1/B1 = 95/5 Example 102 Z36 (80) Comparative (16)  Z6(40) 3 W-1 A1/B1 = 95/5 Example 103 Z39 (80) Comparative (17)  Z6 (45) 3W-1 A1/B1 = 95/5 Example 104

The abbreviations used in Tables 105 to 107 are described below.

The acid generators are selected from Z1 to Z40 in the specific examplesof component (A) described hereinbefore.

The abbreviations of the basic compounds are as follows. The ratio ofbasic compounds in case of using two or more thereof shown in Tables 105to 107 is indicated by a weight ratio.

-   C1: Tridecylamine-   C2: Tetradecylamine-   C3: Pentadecylamine-   C4: Hexadecylamine-   C5: Octadecylamine-   C6: Didecylamine-   C7: Methyloctadecylamine-   C8: Triisodecylamine-   C9: N,N-Dimethylundecylamine-   C10: N,N-Dimethyldodecylamine-   C11: Tridodecylamine-   C12: MethyldiQctadecylamine-   C13: Trioctylamine-   1: 1,5-Diazabicyclo[4.3.0]non-5-ene-   2: Bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate-   3: Tri-n-butylamine-   4: Triphenylimidazole-   5: Antipyrine-   6: 2,6-Diisopropylaniline

The abbreviations of the surface active agents are as follows.

-   W-1: Megafax F176 (manufactured by Dainippon Ink and Chemicals,    Inc.) (fluorine-base)-   W-2: Megafac R08 (manufactured by Dainippon Ink and Chemicals, Inc.)    (fluorine- and silicon-base)-   W-3: Polysiloxane Polymer KP-341 (manufactured by Shin-Etsu Chemical    Co., Ltd.) (silicon-base)-   W-4: Troysol S-366 (manufactured by Troy Chemical Co., Ltd.)

The abbreviations of the solvents are as. follows. The ratio of solventsin case-of using two or more thereof shown in Tables 105 to 107 isindicated by a weight ratio,

-   A1: Propylene glycol methyl ether acetate-   A2: 2-Heptanone-   A3: Ethyl ethoxypropionate-   A4: γ-Sutyrolactone-   A5: Cyclohexanone-   B1: Propylene glycol methyl ether-   B2: Ethyl lactate    <Evaluation of Pattern>    (1) Evaluation of Fluctuation in Linewidth

The evaluation of fluctuation in linewidth was conducted in the samemanner as in Examples 1 to 76 and Comparative Examples 1 to 4.

(2) Evaluation of Sidelobe Resistance

On a silicon substrate which had been subjected to ahexamethyldisilazane treatment was uniformly coated a reflectionpreventing film (DUV-42 manufactured by Brewer Science, Inc.) at athickness of 600 angstroms by a spin coater, dried at 100° C. for 90seconds on a hot plate, and further dried by heating at 190° C. for 240seconds. Thereafter, each of the photosensitive compositions describedabove was coated thereon by a spin coater and dried at 120° C. for 90seconds to form a resist film having a thickness of 0.30 μm. The resistfilm was subjected to exposure using an ArF excimer laser stepper(manufacture by ISI Co., Ltd.; NA=0.6) through a mask. and heated at120° C. for 90 seconds on a hot plate immediately after the exposure.Then the resist film was developed with a 2.38% by weight aqueoustetramethylammonium hydroxide solution at 23° C. for 60 seconds, rinsedwith pure water for 30 seconds, and dried to obtain a resist pattern.

The evaluation of sidelqbe resistance was conducted by resolving 0.22 μmto 0.20 μm using a halftone phase sift mask and observing a pattern of0.18 μm. The pattern wherein the occurrence of sidelobe was notrecognized was indicated by Al the pattern wherein the occurrence ofsidelobe was slightly recognized was indicated by B, and the patternwherein the occurrence of sidelobe was clearly recognized was indicatedby C. TABLE 108 Fluctuation in Sidelobe Example Linewidth (mμ)Resistance 101 0.002 A 102 0.002 A 103 0.002 A 104 0.002 A 105 0.002 A106 0.003 A 107 0.002 B 108 0.003 A 109 0.002 A 110 0.002 A 111 0.002 A112 0.003 A 113 0.002 A 114 0.002 A 115 0.003 A 116 0.002 A 117 0.002 A118 0.002 A 119 0.002 A 120 0.003 A 121 0.002 A 122 0.003 A 123 0.002 A124 0.003 A 125 0.002 A

TABLE 109 Fluctuation in Sidelobe Example Linewidth (mμ) Resistance 1260.002 A 127 0.003 A 128 0.002 A 129 0.002 A 130 0.002 A 131 0.003 A 1320.002 A 133 0.002 A 134 0.002 A 135 0.002 A 136 0.002 A 137 0.002 A 1380.003 A 139 0.003 A 140 0.002 A 141 0.002 A 142 0.002 A 143 0.002 A 1440.002 A 145 0.002 A 146 0.003 A 147 0.002 A 148 0.002 A 149 0.003 A 1500.002 A

TABLE 110 Fluctuation in Sidelobe Example Linewidth (mμ) Resistance 1510.002 B 152 0.002 A 153 0.003 A 154 0.003 A 155 0.002 A 156 0.002 A 1570.002 A 158 0.002 A 159 0.003 A 160 0.003 A 161 0.003 A 162 0.002 A 1630.002 A 164 0.003 A 165 0.002 A 166 0.003 A 167 0.002 A 168 0.002 A 1690.003 A 170 0.002 A 171 0.002 A 172 0.003 A 173 0.002 A 174 0.002 A 1750.002 A 176 0.002 A Comparative 0.01 C Example 101 Comparative 0.01 CExample 102 Comparative 0.01 C Example 103 Comparative 0.01 C Example104

From the results shown in Tables 108 to 110, it can be seen that thephotosensitive compositions of Examples 101 to 176 exhibit the excellentsidelobe resistance (halftone exposure aptitude) as well as the smallfluctuation in linewidth.

Examples 201 to 276 and Comparative Examples 201 to 204

<Preparation of Photosensitive Composition>

In each of Examples 201 to 276 and Comparative Examples 201 to 204, thecomponents as shown in Tables 205 to 207 below were dissolved to preparea solution having a solid concentration of 12% by weight. The resultingsolution was filtered through a Teflon filter having a pore size of 0.1μm, whereby a positive photosensitive composition was prepared.

The photosensitive composition was evaluated by the methods describedbelow. The results obtained are shown in Tables 208 to 210 below. TABLE205 Surface Acid Basic Active Solvent Resin Generator Compound Agent(weight Example (10 g) (mg) (0.03 g) (0.03 g) ratio) 201  (1) Z2 (45) C1W-1 A1/B1 = 95/5 202  (2) Z2 (45) C2 W-1 A1 = 100 203  (3) Z3 (45) C3W-2 A1/B1 = 90/10 204  (4) Z8 (47) C4 W-2 A2/B2 = 80/20 205  (5) Z5 (43)C5 W-3 A2/B1 = 90/10 206  (6) Z19 (90) C3 W-3 A4/B1 = 90/10 207  (7) Z20(90) C4 W-4 A1/B1 = 50/50 208  (8) Z21 (95) C5 W-4 A1/B1 = 90/10 209 (9) Z21 (98) C3 W-1 A5/B2 = 90/10 210 (10) Z34 (45) C4 W-1 A1/B1 = 95/5211 (11) Z31 (75) C5 W-2 A1/B1 = 90/10 212 (12) Z38 (90) C3/Ca = 1/1 W-2A1/B1 = 95/5 213 (13) Z2 (30) C3/Ca = 1/1 W-3 A1/B1 = 95/5 Z31 (50) 214(14) Z3 (30) C4/Cb = 1/1 W-3 A1/B1 = 95/5 Z38 (50) 215 (15) Z2 (30)C5/Cc = 1/1 W-4 A1/B1 = 80/20 Z38 (45) 216 (16) Z31 (95) C3/Cd = 1/1 W-4A1/B1 = 80/20 217 (17) Z40 (90) C4/Cc = 1/1 W-4 A1/B1 = 95/5 218 (18)Z36 (90) C3 W-4 A1/B1 = 95/5 219 (19) Z19 (60) C4 W-4 A1/B1 = 95/5 Z14(30) 220 (20) Z2 (45) C3 W-4 A1/B1 = 95/5 221 (21) Z2 (45) C3 W-1 A1/B1= 95/5 222 (22) Z19 (90) C4 W-1 A1/B1 = 80/20 223 (23) Z2 (40) C3 W-2A1/B1 = 90/10 Z11 (40) 224 (24) Z13 (43) C5 W-2 A3/B2 = 80/20 225 (25)Z13 (45) C3/Ca = 1/1 W-3 A2/B1 = 90/10 Z12 (20)

TABLE 206 Surface Acid Basic Active Solvent Resin Generator CompoundAgent (weight Example (10 g) (mg) (0.03 g) (0.03 g) ratio) 226 (26) Z8(45) C3/Ca = 1/1 W-3 A4/B1 = 90/10 227 (27) Z8 (45) C4/Cb = 1/1 W-4A1/B1 = 50/50 228 (28) Z8 (45) C5/Cd = 1/1 W-4 A1/B1 = 90/10 Z12 (20)229 (29) Z30 (60) C1/Cd = 1/1 W-1 A5/B2 = 90/10 Z26 (20) 230 (30) Z30(70) C3 W-1 A1/B1 = 95/5 Z27 (20) 231 (31) Z8 (40) C4 W-2 A1/B1 = 90/10Z29 (30) 232 (32) Z33 (40) C5 W-2 A1/B1 = 95/5 233 (33) Z34 (40) C1 W-3A1/B1 = 95/5 234 (34) Z33 (40) C2 W-3 A1/B2 = 95/5 Z30 (20) 235 (35) Z33(40) C3/Ca = 1/1 W-4 A1/B1 = 80/20 Z30 (20) 236 (36) Z34 (40) C5/Cd =1/1 W-4 A1/B1 = 80/20 Z36 (80) 237 (37) Z40 (60) C4/Cc = 1/1 W-4 A1/B1 =95/5 Z34 (20) 238 (38) Z38 (40) C3 W-4 A1/B1 = 95/5 Z33 (40) 239 (39)Z23 (50) C1 W-4 A1/B1 = 95/5 Z30 (30) 240 (40) Z2 (45) C4 W-4 A1/B1 =95/5 Z7 (20) 241 (41) Z9 (45) C2 W-1 A1/B1 = 95/5 242 (42) Z10 (45)C3/C2 = 1/1 W-1 A1/B1 = 80/20 243 (43) Z2 (35) C4/C3 = 1/1 W-2 A1/B1 =90/10 Z1 (10) 244 (44) Z6 (40) C3/Cd = 1/1 W-2 A3/B2 = 80/20 245 (45) Z6(30) C4/Cb = 1/1 W-3 A2/B1 = 90/10 Z1 (15) 246 (46) Z16 (40) C3/Cd = 1/1W-3 A4/B1 = 90/10 247 (47) Z2 (45) C4/Cc = 1/1 W-4 A1/B1 = 50/50 Z18(10) 248 (48) Z19 (40) C2 W-4 A1/B1 = 90/10 Z20 (40) 249 (49) Z8 (45) C4W-1 A5/B2 = 90/10 Z12 (20) 250 (50) Z33 (40) C3 W-1 A1/B1 = 95/5

TABLE 207 Surface Basic Active Solvent Acid Generator Compound Agent(weight Example Resin (10 g) (mg) (0.03 g) (0.03 g) ratio) 251 (51) Z30(60) C4 W-2 A1/B1 = 90/10 Z26 (20) 252 (52) Z33 (40) C3 W-2 A1/B1 = 95/5253 (53) Z33 (40) C1 W-3 A1/B1 = 95/5 Z30 (20) 254 (54) Z40 (60) C3 W-3A1/B1 = 95/5 Z34 (20) 255 (55) Z23 (50) C3/C5 = 1/1 W-4 A1/B1 = 80/20Z30 (30) 256 (56) Z9 (45) C3/Ca = 1/1 W-4 A1/B1 = 80/20 257 (57) Z9 (45)C4/Cc = 1/1 W-4 A1/B1 = 95/5 258 (58) Z2 (35) C5/Cb = 1/1 W-4 A1/B1 =95/5 Z1 (10) 259 (59) Z6 (50) C3/Ca = 1/1 W-4 A1/B1 = 95/5 260 (60) Z16(40) C4 W-4 A1/B1 = 95/5 261 (61) Z2 (45) C4 W-1 A1/B1 = 95/5 Z18 (10)262 (62) Z33 (40) C3 W-1 A1/B1 = 80/20 263 (63) Z8 (45) C3/Cb = 1/1 W-2A1/B1 = 90/10 Z12 (20) 264 (64) Z16 (40) C2/Ca = 1/1 W-2 A3/B2 = 80/20265 (65) Z2 (45) C4/Cc = 1/1 W-3 A2/B1 = 90/10 Z20 (20) 266 (66) Z8 (45)C3/Cc = 1/1 W-3 A4/B1 = 90/10 Z12 (20) 267 (67) Z23 (50) C5/Cc = 1/1 W-1A1/B1 = 90/10 Z30 (30) 268 (68) Z33 (40) C4/Cd = 1/1 W-1 A1/B1 = 95/5269 (69) Z30 (40) C4/Cc = 1/1 W-4 A1/B1 = 90/10 Z26 (20) 270 (16) Z9(45) C3/Cd = 1/1 W-4 A1/B1 = 80/20 271 (16) Z31 (95) C4/Ca = 1/1 W-3A2/B1 = 90/10 272 (16) Z40 (90) C4 W-2 A1/B1 = 95/5 273 (16) Z36 (90) C3W-1 A1/B1 = 95/5 274 (17) Z2 (45) C4 W-3 A1/B1 = 90/10 Z12 (20) 275 (17)Z2 (45) C4 W-2 A1/B1 = 90/10 Z12 (20) 276 (17) Z14 (45) C4 W-1 A1/B1 =80/20 Z22 (20) Comparative  (1) Z6 (45) Ca W-1 A1/B1 = 95/5 Example 201Comparative (13) Z6 (40) Ca W-1 A1/B1 = 95/5 Example 202 Z36 (80)Comparative (16) Z6 (40) Cc W-1 A1/B1 = 95/5 Example 203 Z39 (80)Comparative (17) Z6 (45) Cc W-1 A1/B1 = 95/5 Example 204

The abbreviations used in Tables 205 to 207 are described below.

The acid generators are selected from Z1 to Z40 in the specific examplesof component (A) described hereinbefore.

The abbreviations of the basic compounds are as follows. The ratio ofbasic compounds in case of using two or more thereof shown in Tables 205to 207 is indicated by a weight ratio.

-   C1: Methoxyethoxyethylamine-   C2: Bis(methoxyethoxyethyl)amine-   C3: Tris(methoxymethoxyethyl)amine-   C4: Tris(methoxyethoxyethyl)amine-   C5: Tris(methoxyethoxymethoxyethyl)amine-   Ca: Tributylamine-   Cb: Trioctylamine-   Cc: 2,6-Diisopropylanilire.-   Cd: 1,5-Diazabicyclo[4.3.0]non-5-ene-   Ce: Antipyrine

The abbreviations of the surface active agents are as follows.

-   W-1: Megafax F176 (manufactured by Dainippon Ink and Chemicals,    Inc.) (fluorine-base)-   W-2: Megafac R08 (manufactured by Dainippon Ink and Chemicals, Inc.)    (fluorine- and silicon-base)-   W-3: Polysiloxane Polymer KP-341 (manufactured by Shin-Etsu Chemical    Co., Ltd.) (silicon-base)-   W-4: Troysol S-366 (manufactured by Troy Chemical Co., Ltd.)

The abbreviations of the solvents are as follows. The ratio of solventsin case of using two or more thereof shown in Tables 205 to 207 isindicated by a weight ratio.

-   A1: Propylene glycol methyl ether acetate-   A2: 2-Heptanone-   A3: Ethyl ethoxypropionate-   A4: γ-Butyrolactone-   A5: Cyclohexanone-   B1: Propylene glycol methyl ether-   B2: Ethyl lactate    <Evaluation of Pattern>    (1) Evaluation of Fluctuation in Linewidth

The evaluation of fluctuation in linewidth was conducted in the samemanner as in Examples 1 to 76 and Comparative Examples 1 to 4.

(2) Evaluation of Development Defect

On a silicon wafer was coated a reflection preventing film (ARC 25manufactured by Brewer Science, Inc.) at a thickness of 30 nm by a spincoater, followed by drying. Then, each of the photosensitivecompositions described above was coated thereon by a spin coater anddried at 115° C. for 90 seconds in each of Examples 201 to 218 andComparative Examples 1 to 2, or at 135° C. for 90 seconds in each ofExamples 219 to 276 and Comparative Examples 203 to 204 to form apositive photoresist film having a thickness of about 0.4 μm. The resistfilm was subjected to exposure using an ArF excimer laser (193 nm)stepper (manufacture by ISI Co., Ltd.) and then heat treatment at 115°C. for 90 seconds in each of Examples 201 to 218 and ComparativeExamples 201 to 202, or at 130° C. for 90 seconds in each of Examples219 to 276 and Comparative Examples 203 to 204. Then the resist film wasdeveloped with a 2.38% by weight aqueous tetramethylammonium hydroxidesolution, rinsed with distilled water, and dried to obtain a resistpattern profile.

With the resist pattern obtained, a number of development defectoccurred was measured by a device (KLA-2112 manufactured by KLA-TencorCorp.). The primary datum was designated as the number of developmentdefect. As the value is smaller, the development defect is better. TABLE208 Number of Fluctuation in Development Example Linewidth (mμ) Defect201 0.002 2 202 0.003 3 203 0.002 2 204 0.002 3 205 0.002 3 206 0.003 2207 0.002 2 208 0.002 2 209 0.003 2 210 0.002 4 211 0.002 1 212 0.003 1213 0.002 2 214 0.002 1 215 0.002 1 216 0.002 1 217 0.002 1 218 0.003 3219 0.002 4 220 0.002 2 221 0.002 3 222 0.002 1 223 0.002 2 224 0.003 4225 0.002 3

TABLE 209 Number of Fluctuation in Development Example Linewidth (mμ)Defect 226 0.002 5 227 0.002 2 228 0.002 1 229 0.003 3 230 0.002 2 2310.003 4 232 0.002 3 233 0.002 1 234 0.002 2 235 0.002 3 236 0.002 2 2370.003 4 238 0.002 2 239 0.003 3 240 0.002 4 241 0.002 3 242 0.003 1 2430.002 2 244 0.002 3 245 0.003 4 246 0.002 2 247 0.002 4 248 0.003 3 2490.003 1 250 0.002 3

TABLE 210 Number of Fluctuation in Development Example Linewidth (mμ)Defect 251 0.002 4 252 0.002 2 253 0.003 3 254 0.003 4 255 0.002 1 2560.002 2 257 0.002 3 258 0.003 4 259 0.002 2 260 0.002 4 261 0.003 1 2620.002 4 263 0.003 3 264 0.002 1 265 0.003 2 266 0.002 4 267 0.002 3 2680.003 1 269 0.003 2 270 0.002 4 271 0.002 2 272 0.002 3 273 0.002 4 2740.002 2 275 0.002 4 276 0.002 3 Comparative 0.01 39 Example 201Comparative 0.01 46 Example 202 Comparative 0.01 38 Example 203Comparative 0.01 46 Example 204

From the results shown in Tables 208 to 210, it can be seen that in thephotosensitive compositions of Examples 201 to 276, the number ofdevelopment defect occurred is very small as well as restraining thefluctuation in linewidth.

The positive photosensitive composition according to the presentinvention exhibits the excellent edge roughness of pattern, theexcellent halftone exposure aptitude and the low occurrence ofdevelopment defect as well as the small fluctuation in linewidth.

The entire disclosure of each and every foreign patent application fromwhich the benefit of foreign priority has been claimed in the presentapplication is incorporated herein by reference, as if fully set forthherein.

While the invention has been described in detail and with reference tospecific examples thereof, it will be apparent to one skilled in the artthat various changes and modifications can be made therein withoutdeparting from the spirit and scope thereof.

1-2. (canceled)
 3. A positive photosensitive composition comprising (A)an acid generator that generates an acid upon irradiation of an actinicray or radiation, (B) a resin that has a monocyclic or polycyclicalicyclic hydrocarbon structure and is decomposed by the action of anacid to increase solubility in an alkali developing solution, and (C-2)a basic compound containing a substituted or unsubstituted aliphatichydrocarbon group having not less than 8 carbon atoms.
 4. A positivephotosensitive composition comprising (A) an acid generator thatgenerates an acid upon irradiation of an actinic ray or radiation, (B) aresin that has a monocyclic or polycyclic alicyclic hydrocarbonstructure and is decomposed by the action of an acid to increasesolubility in an alkali developing solution, and (C-3) a basic compoundselected from an oxygen-containing primary aliphatic amine, anoxygen-containing secondary aliphatic amine and an oxygen-containingtertiary aliphatic amine.
 5. The positive photosensitive composition asclaimed in claim 4, wherein the positive photosensitive compositionfurther comprises (C′) a basic compound that does not contain an oxygenatom.
 6. The positive photosensitive composition as claimed in claim 3,wherein the positive photosensitive composition further comprises (D) afluorine and/or silicon surface active agent.
 7. The positivephotosensitive composition as claimed in claim 3, wherein the positivephotosensitive composition further comprises (F) a dissolutioninhibiting low molecular weight compound having a group capable of beingdecomposed by the action of an acid to increase solubility in an alkalideveloping solution and having a molecular weight of not more than3,000.
 8. The positive photosensitive composition as claimed in claim 3,wherein the positive photosensitive composition further comprises (E) amixed solvent composed of a solvent containing a hydroxy group and asolvent containing no hydroxy group.
 9. The positive photosensitivecomposition as claimed in claim 3, wherein the resin of component (B) isa resin containing at least one repeating unit selected from a repeatingunit having a partial structure including an alicyclic hydrocarbonrepresented by formula (pI), (pII), (pIII), (pIV), (pV) or (pVI)described below and a repeating unit represented by formula (II-AB)described below.

wherein R₁₁ represents a methyl group, an ethyl group, an n-propylgroup, an isopropyl group, an n-butyl group, an isobutyl group or asec-butyl group; Z represents an atomic group necessary for forming analicyclic hydrocarbon group together with the carbon atom; R₁₂ to R₁₆each independently represent a straight chain or branched alkyl grouphaving from 1 to 4 carbon atoms or an alicyclic hydrocarbon group,provided that at least one of R₁₂ to R₁₄, and either R₁₅ or R₁₆represents an alicyclic hydrocarbon group; R₁₇ to R₂₁ each independentlyrepresent a hydrogen atom, a straight chain or branched alkyl grouphaving from 1 to 4 carbon atoms or an alicyclic hydrocarbon group,provided that at least one of R₁₇ to R₂₁ represents an alicyclichydrocarbon group, and either R₁₉ or R₂₁ represents a straight chain orbranched alkyl group having from 1 to 4 carbon atoms or an alicyclichydrocarbon group; and R₂₂ to R₂₅ each independently represent astraight chain or branched alkyl group having from 1 to 4 carbon atomsor an alicyclic hydrocarbon group, provided that at least one of R₂₂ toR₂₅ represents an alicyclic hydrocarbon group, or R₂₃ and R₂₄ may becombined with each other to form a ring,

wherein R₁₁′ and R₁₂′, which may be the same or different, eachindependently represent a hydrogen atom, a cyano group, a halogen atomor an alkyl group which may have a substituent; and Z′ represents anatomic group necessary for forming an alicyclic structure, which may besubstituted, together with the connected two carbon atoms (C—C).
 10. Thepositive photosensitive composition as claimed in claim 9, wherein therepeating unit represented by formula (II-AB) is a repeating unitrepresented by the following formula (II-A) or (II-B):

wherein R₁₃′ to R₁₆′, which may be the same or different, eachindependently represents a hydrogen atom, a halogen atom, a cyano group,—COOH, —COOR₅, a group capable of decomposing by the action of acid,—C(═O)—X-A′-R₁₇′, an alkyl group which may have a substituent or acyclic hydrocarbon group which may have a substituent; R₅ represents analkyl group which may have a substituent, a cyclic hydrocarbon groupwhich may have a substituent or a group represented by Y; X representsan oxygen atom, a sulfur atom, —NH—, —NHSO₂— or —NHSO₂NH—; A′ representsa single bond or a divalent linkage group, or at least two of R₁₃′ toR₁₆′ may be combined with each other to form a ring; n represents 0 or1; R₁₇′ represents —COOH, —COOR₅, —CN, a hydroxy group, an alkoxy groupwhich may have a substituent, —CO—NH—R₆, —CO—NH—SO₂—R₆ or a grouprepresented by Y; R₆ represents an alkyl group which may have asubstituent or a cyclic hydrocarbon group which may have a substituent;and the group represented by Y has the following structure:

wherein R₂₁′ to R₃₀′, which may be the same or different, eachindependently represents a hydrogen atom or an alkyl group which mayhave a substituent; and a and b each represent 1 or
 2. 11. The positivephotosensitive composition as claimed in claim 3, wherein the resin ofcomponent (B) is a resin containing a repeating unit having a lactonestructure represented by the following formula (IV):

wherein R_(1a) represents a hydrogen atom or a methyl group; W₁represents a single bond, an alkylene group, an ether group, a thioethergroup, a carbonyl group, an ester group or a combination of two or morethereof; R_(a1), R_(b1), R_(c1), R_(d1) and R_(e1), which may be thesame or different, each independently represent a hydrogen atom or analkyl group having from 1 to 4 carbon atoms; and m and n, which may bethe same or different, each independently represent an integer of from 0to 3, provided that the sum total of m and n is from 2 to
 6. 12. Thepositive photosensitive composition as claimed in claim 3, wherein theresin of component (B) is a resin containing a repeating unit having agroup represented by any one of the following formulae (V-1) to (V-4):

wherein R_(1b), R_(2b), R_(3b), R_(4b) and R_(5b), which may be the sameor different, each represent a hydrogen atom, an alkyl group which maybe substituted, a cycloalkyl group which may be substituted or analkenyl group which may be substituted, or two of R_(1b), R_(2b),R_(3b), R_(4b) and R_(5b) may be combined with each other to form aring.
 13. The positive photosensitive composition as claimed in claim 3,wherein the resin of component (B) further contains a repeating unithaving a group represented by the following formula (VI):

wherein A₆ represents a single bond, an alkylene group, a cycloalkylenegroup, an ether group, a thioether group, a carbonyl group, an estergroup or a combination of two or more thereof, R_(6a) represents ahydrogen atom, an alkyl group having from 1 to 4 carbon atoms, a cyanogroup or a halogen atom.
 14. The positive photosensitive composition asclaimed in claim 3, wherein the resin of component (B) further containsa repeating unit having a group represented by the following formula(VII):

wherein R_(2c), R_(3c), and R_(4c), which may be the same or different,each represent a hydrogen atom or a hydroxy group, provided that atleast one of R₂C, R₃c and R₄c represents a hydroxy group.
 15. Thepositive photosensitive composition as claimed in claim 3, wherein theresin of component (B) further contains a repeating unit having a grouprepresented by the following formula (VIII):

wherein Z₂ represents —O— or —N(R₄₁)—; R_(4,) represents a hydrogenatom, a hydroxy group, an alkyl group, a haloalkyl group or —O—SO₂—R₄₂;and R₄₂ represents an alkyl group, a haloakyl group, a cycloalkyl groupor a camphol residue.
 16. (canceled)
 17. The positive photosensitivecomposition as claimed in claim 4, wherein the positive photosensitivecomposition further comprises (D) a fluorine and/or silicon surfaceactive agent.
 18. The positive photosensitive composition as claimed inclaim 4, wherein the positive photosensitive composition furthercomprises (F) a dissolution inhibiting low molecular weight compoundhaving a group capable of being decomposed by the action of an acid toincrease solubility in an alkali developing solution and having amolecular weight of not more than 3,000.
 19. The positive photosensitivecomposition as claimed in claim 4, wherein the positive photosensitivecomposition further comprises (E) a mixed solvent composed of a solventcontaining a hydroxy group and a solvent containing no hydroxy group.20. The positive photosensitive composition as claimed in claim 4,wherein the resin of component (B) is a resin containing at least onerepeating unit selected from a repeating unit having a partial structureincluding an alicyclic hydrocarbon represented by formula (pI), (pII),(pIII), (pIIV), (pV) or (pVI) described below and a repeating unitrepresented by formula (II-AB) described below.

wherein R₁₁ represents a methyl group, an ethyl group, an n-propylgroup, an isopropyl group, an n-butyl group, an isobutyl group or asec-butyl group; Z represents an atomic group necessary for forming analicyclic hydrocarbon group together with the carbon atom; R₁₂ to R₁₆each independently represent a straight chain or branched alkyl grouphaving from 1 to 4 carbon atoms or an alicyclic hydrocarbon group,provided that at least one of R₁₂ to R₁₄, and either R₁₅ or R₁₆represents an alicyclic hydrocarbon group; R₁₇ to R₂₁ each independentlyrepresent a hydrogen atom, a straight chain or branched alkyl grouphaving from 1 to 4 carbon atoms or an alicyclic hydrocarbon group,provided that at least one of R₁₇ to R₂₁ represents an alicyclichydrocarbon group, and either R₁₉ or R₂₁ represents a straight chain orbranched alkyl group having from 1 to 4 carbon atoms or an alicyclichydrocarbon group; and R₂₂ to R₂₅ each independently represent astraight chain or branched alkyl group having from 1 to 4 carbon atomsor an alicyclic hydrocarbon group, provided that at least one of R₂₂ toR₂₅ represents an alicyclic hydrocarbon group, or R₂₃ and R₂₄ may becombined with each other to form a ring,

wherein R₁₁′ and R₁₂′, which may be the same or different, eachindependently represent a hydrogen atom, a cyano group, a halogen atomor an alkyl group which may have a substituent; and Z′ represents anatomic group necessary for forming an alicyclic structure, which may besubstituted, together with the connected two carbon atoms (C—C).
 21. Thepositive photosensitive composition as claimed in claim 20, wherein therepeating unit represented by formula (II-AB) is a repeating unitrepresented by the following formula (II-A) or (II-B):

wherein R₁₃′ to R₁₆′, which may be the same or different, eachindependently represents a hydrogen atom, a halogen atom, a cyano group,—COOH, —COOR₅, a group capable of decomposing by the action of acid,—C(═O)—X-A′-R₁₇′, an alkyl group which may have a substituent or acyclic hydrocarbon group which may have a substituent; R₅ represents analkyl group which may have a substituent, a cyclic hydrocarbon groupwhich may have a substituent or a group represented by Y; X representsan oxygen atom, a sulfur atom, —NH—, —NHSO₂— or —NHSO₂NH—; A′ representsa single bond or a divalent linkage group, or at least two of R₁₃′ toR₁₆′ may be combined with each other to form a ring; n represents 0 or1; R₁₇′ represents —COOH, —COOR₅, —CN, a hydroxy group, an alkoxy groupwhich may have a substituent, —CO—NH-R₆, —CO—NH—SO₂—R₆ or a grouprepresented by Y; R₆ represents an alkyl group which may have asubstituent or a cyclic hydrocarbon group which may have a substituent;and the group represented by Y has the following structure:

wherein R₂₁′ to R₃₀′, which may be the same or different, eachindependently represents a hydrogen atom or an alkyl group which mayhave a substituent; and a and b each represent 1 or
 2. 22. The positivephotosensitive composition as claimed in claim 4, wherein the resin ofcomponent (B) is a resin containing a repeating unit having a lactonestructure represented by the following formula (IV):

wherein R_(1a) represents a hydrogen atom or a methyl group; W₁represents a single bond, an alkylene group, an ether group, a thioethergroup, a carbonyl group, an ester group or a combination of two or morethereof, R_(a1), R_(b1), R_(c1), R_(d1) and R_(e1), which may be thesame or different, each independently represent a hydrogen atom or analkyl group having from 1 to 4 carbon atoms; and m and n, which may bethe same or different, each independently represent an integer of from 0to 3, provided that the sum total of m and n is from 2 to
 6. 23. Thepositive photosensitive composition as claimed in claim 4, wherein theresin of component (B) is a resin containing a repeating unit having agroup represented by any one of the following formulae (V-1) to (V-4):

wherein R_(1b), R_(2b), R_(3b), R_(4b) and R_(5b), which may be the sameor different, each represent a hydrogen atom, an alkyl group which maybe substituted, a cycloalkyl group which may be substituted or analkenyl group which may be substituted, or two of R_(1b), R_(2b),R_(3b), R_(4b) and R_(5b) may be combined with each other to form aring.
 24. The positive photosensitive composition as claimed in claim 4,wherein the resin of component (B) further contains a repeating unithaving a group represented by the following formula (VI):

wherein A₆ represents a single bond, an alkylene group, a cycloalkylenegroup, an ether group, a thioether group, a carbonyl group, an estergroup or a combination of two or more thereof; R_(6a) represents ahydrogen atom, an alkyl group having from 1 to 4 carbon atoms, a cyanogroup or a halogen atom.
 25. The positive photosensitive composition asclaimed in claim 4, wherein the resin of component (B) further containsa repeating unit having a group represented by the following formula(VII):

wherein R_(2c), R_(3c), and R_(4c), which may be the same or different,each represent a hydrogen atom or a hydroxy group, provided that atleast one of R_(2c), R_(3c), and R_(4c) represents a hydroxy group. 26.The positive photosensitive composition as claimed in claim 4, whereinthe resin of component (B) further contains a repeating unit having agroup represented by the following formula (VIII):

wherein Z₂ represents —O— or —N(R₄₁)—; R₄ represents a hydrogen atom, ahydroxy group, an alkyl group, a haloalkyl group or —O—SO₂—R₄₂; and R₄₂represents an alkyl group, a haloakyl group, a cycloalkyl group or acamphol residue.